Heterogeneous alkoxylation using anion-bound metal oxides

ABSTRACT

Active-hydrogen compounds, for example, primary and secondary alcohols or diols, are alkoxylated, for example, ethoxylated, using solid anion-bound metal oxide catalysts, such as, zirconium oxysulfate catalyst. Hydrous zirconium oxide is treated with solutions of sulfate phosphate, nitrate or tetrafluoroborate and calcined in air at 300° to 950° C. to produce highly active heterogeneous alkoxylation catalysts. The amorphous catalysts afford narrow molecular weight products. The catalyst can be removed from the product by filtration and reused with no significant loss in activity. Reaction temperatures of 50° to 140° C. are employed for alkoxylation.

This application is a division of prior U.S. application Ser. No.119,690, filing date Nov. 12, 1987, now U.S. Pat. No. 4,873,017 which isa division of application Ser. No. 753,543, filing date July 10, 1985,now U.S. Pat. No. 4,727,199.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The invention relates to a catalytic process of alkoxylatingactive-hydrogen compounds, to the starting compositions and to thealkoxylation catalysts.

2. Background Art

Hino, Makoto, and Kazushi Arata, "Synthesis of Solid Superacid Catalystwith Acid Strength of H₀ <-16.04", J. C. S. Chem. Comm., (1980) pages851 and 852, discloses a solid superacid catalyst with an acid strengthof H₀ <-16.04. The catalyst was obtained by exposing Zr(OH)₄, preparedby the hydrolysis of ZrOCl₂, to 1N H₂ SO₄ and then calcining it in airat 575° to 650° C.

Hino, Makoto, and Kazushi Arata, "Synthesis Of Esters From Acetic AcidWith Methanol, Ethanol, Propanol, Butanol, And Isobutyl AlcoholCatalyzed By Solid Superacid", Chemical Letters, Chem. Soc. Jap.,(1981), pages 1671 and 1672, discloses catalytically esterifying aceticacid with lower alkanols, such as, ethanol. A solid superacid catalyst,which was obtained by exposing Zr(OH)₄ to 1N H₂ SO₄ and then calciningin air at 500° to 750° C., was stated to be highly active for theheterogeneous esterification reactions at 30° to 45° C. The reactionswith used catalysts gave identical results with those using freshlyactivated catalysts. (Esterification reactions are known to be catalyzedby acids.) Solid superacid catalysts were also prepared from Fe(OH)₃ andH₄ TiO₄.

Hino, M., and K. Arata, "Conversion Of Pentane To Isopentane AndIsopentane To Isobutane Catalyzed By A Solid Superacid In The VaporPhase", React. Kinct. Catal. Lett., Vol. 19, No. 1-2, (1982), pages 101to 104, discloses converting pentane and isopentane, respectively, intoisopentane and isobutane using a solid superacid, which was prepared byexposing Zr(OH)₄ to 1N H₂ SO₄, followed by calcination at 650° C. inair. The selectivities were 84 percent under short contact conditions at80° C. The reactions involved the isomerization and hydrocracking oflower hydrocarbons. The paper states that Takahashi et al. preparedsolid superacids by supporting SbF₅ on metal oxides and studiedreactions of pentane and isopentane. [R. Ohnishi T., Morikawa, Y. Hiragaand K. Tanabe, Zeitschrift fur Physikalische Chemic Nue Folg, Vol. 130,pp. 205-209, (1982)]

The above-discussed Hino and Arata articles are inconsistent and teachaway from the invention which is the subject of this application.

Chukhlantsev, V. G., and Yu. M. Galkin, "Thermal Decomposition Of BasicZirconium Sulphate", Russian Journal of Inorganic Chemistry, 18 (6),(1973), pages 770 and 771, earlier disclosed that when basic zirconiumsulphate is heated to 500° to 650° C. (even above 400° to 420° C.) onlydehydration, accompanied by the formation of an anhydrous productamorphous to X-rays, took place. Starting from 600° C. the latterdecomposed with the formation of ZrO₂ and release of SO₃. Basiczirconium sulfate was obtained by boiling a solution of zirconium oxidechloride containing 50 g of ZrO₂ per liter, 15 g of free HCl per liter,and sulfuric acid to give SO₃ : ZrO₂ =0.56 (molar). The product waswashed and then dried at 100° C.

The Condensed Dictionary, 10th Ed., (1981) pages 1115 to 1117,discloses: Zr₅ O₈ (SO₄)₂.xH₂ O, zirconyl sulfate on zirconium sulfate,basic; ZrOCO₃.xH₂ O, zirconyl carbonate or zirconium carbonate, basic;ZrOCl₂.8H₂ O, zirconyl chloride or zirconium oxychloride; ZrO(OH)Cl._(n)H₂ O, zirconyl hydroxychloride; and ZrO(OH)NO₃, zirconyl hydroxynitrateor zirconyl nitrate, basic. Zirconium oxychloride can be prepared by theaction of hydrochloric acid on zirconium oxide. Zirconyl sulfate can beprepared in a similar manner. Zr(OH)₄ can be prepared by the action of asolution of sodium hydroxide on a solution of a zirconium salt.

Ethylene oxide, also termed oxirane, has been reacted with C₂ H₅ OH toproduce C₂ H₅ OCH₂ CH₂ OH. The same reaction with ethylene sulfide isknown.

BROAD DESCRIPTION OF THE INVENTION

The invention involves the basic and unexpected discovery thatanion-bound zirconium oxides and certain other anion-bound metal oxidesare heterogeneous catalysts for alkoxylation, particularly ethoxylation.The invention process is broadly the use of anion-bound metal oxideheterogeneous catalysts for the alkoxylation of active-hydrogencompounds, such as, primary or secondary alcohols and diols. Anion-boundzirconium oxide heterogeneous catalysts are highly active.

The invention process for the alkoxylation of active-hydrogen compoundsincludes reacting a liquid or solid reactive epoxide compound having theformula: ##STR1## wherein R₁, R₂, R₃ and R₄ are each H or --(CH₂)_(n)CH₃, and wherein n is 0 to 3, with the proviso that R₁, R₂, R₃ and R₄can be the same or different, with an active-hydrogen compound, theactive-hydrogen compound being in the liquid or gaseous state, in thepresence of a catalytic amount of at least one solid anion-bound metaloxide catalyst. The anion-bound metal oxide catalyst is an amorphous orprimarily amorphous compound. The active-hydrogen compound is one whichdoes not poison the catalyst. The preferred active-hydrogen compound ispreferably a primary monohydric alcohol, a secondary monohydric alcohol,a dihydric alcohol, a trihydric alcohol, a polyhydric alcohol, analkoxylated ethylene glycol or a glycol ether. Water can be used as theactive hydrogen compound. The molar ratio of the cyclic epoxide compoundto the active-hydrogen compound is usually between 3:1 and 1:3. Theprocess is especially advantageous in the ethoxylation of ethyleneglycol.

In the processes of the invention, the preferred epoxide compound isethylene oxide. Also preferably the reaction is continuously conductedin a fixed-bed reactor or a fluidized reactor. Also in the processes ofthe invention, preferably 0.5 to 50 weight percent, based on the totalweight of the cyclic epoxide compound and the other reactant orreactants, of the solid anion-bound metal oxide catalyst is used.Preferably the anion in the anion-bound metal oxide catalyst is SO₄,BF₄, CO₃, BO₃, HPO₄, SeO₄, MoO₄, B₄ O₇ or PF₆, and the metal oxide inthe anion-bound metal oxide catalyst is zirconium oxide, nickel oxide,aluminum oxide, tin oxide, magnesium oxide, rubidium oxide, titaniumoxide, thorium oxide, hafnium oxide or iron oxide. ZrO will readily bindwith anions other than SO₄ ; whereas the other metal oxides will readilybind with SO₄ but not as readily with the other anions. Preferably thecatalyst is a solid sulfate-bound zirconium oxide catalyst, a solidsulfate-bound thorium oxide catalyst or a solid sulfate-bound hafniumoxide catalyst. Although not preferred, the reactants can be used ininert liquid diluents such as hydrocarbons. Normally, the catalyst canbe reused with good selectivity. If necessary, the solid anion-boundmetal oxide catalyst can be removed from the reaction site and can beregenerated by calcination in air or oxygen at a temperature of 300° to950° C. for a period of 1 to 4 hours.

An advantage of the invention process is that it produces a narrowmolecular range of products with a minimum of undesirable high molecularweight co-products or by-products.

The polyoxyethylation of an alcohol is a process of reacting an alcoholwith ethylene oxide to produce a polyether, as in the reaction below, inwhich R of the alcohol can be aliphatic or aromatic: ##STR2## The numberof moles (n) of ethylene oxide reacted can range from 1 to greater than200. The reaction occurs by a stepwise addition of the polymerizationprocess usually catalyzed by acids or bases. The average molecularweight of the product alcohols is determined by the moles of ethyleneoxide reacted compared to the moles of hydroxyl groups in the startingalcohol. The product can contain significant amounts of unreactedstarting alcohol, depending on the relative reactivity of the startingalcohol compared to the reactivity of the product alcohols. Allunhindered hydroxyl groups of monohydric and polyhydric alcohols react,but some may be more reactive than others. The process temperaturesusually range from 80° to 180° C. with the pressure at a level (e.g., 20to 100 p.s.i.g.) needed to maintain conditions in the reactor. Often anexcess of alcohol and/or cyclic epoxide is used.

The invention also involves a composition containing (a) a liquid orsolid epoxide compound having the formula: ##STR3## wherein R₁, R₂, R₃and R₄ are each H or --(CH₂)_(n) CH₃, and wherein n is 0 to 3, with theproviso that R₁, R₂, R₃ and R₄ can be the same or different, (b) anactive-hydrogen compound, such as, a secondary monohydric alcohol, adihydric alcohol, a trihydric alcohol, a polyhydric alcohol, analkoxylated ethylene glycol or a glycol ether, the active-hydrogencompound being in the gaseous or liquid state, and (c) a catalyticamount of at least one solid anion-bound metal oxide catalyst. Theanion-bound metal oxide catalyst is an amorphous or primarily amorphouscompound. The active-hydrogen compound is one which does not poison thecatalyst.

The invention further involves reacting at least one molecule of aliquid or solid epoxide compound having the formula: ##STR4## whereinR₁, R₂, R₃ and R₄ are each H or --(CH₂)_(n) CH₃, and wherein n is 0 to3, with the proviso that R₁, R₂, R₃ and R₄ can be the same or different,with at least one other molecule of the above-identified liquid or solidepoxide compound in the presence of a catalytic amount of at least onesolid anion-bound metal oxide catalyst. The molecules of epoxidecompound can be the same epoxide compound or different epoxide compouds.The anion-bound metal oxide catalyst is an amorphous or primarilyamorphous compound.

The invention still further involves a composition including (a) atleast one liquid or gaseous epoxide compound having the formula:##STR5## wherein R₁, R₂, R₃ and R₄ are each H or --(CH₂)_(n) CH₃, andwherein n is 0 to 3, with the proviso that R₁, R₂, R₃ and R₄ can be thesame or different, and (b) a catalytic amount of at least one solidanion-bound metal oxide catalyst. The anion-bound metal oxide catalystis an amorphous or primarily amorphous compound.

The invention also involves the alkoxylation process of reacting anepoxide compound having the formula: ##STR6## wherein R₁, R₂, R₃ and R₄are each H or --(CH₂)_(n) CH₃, and wherein n is 0 to 3, with the provisothat R₁, R₂, R₃ and R₄ can be the same or different, with a sodium saltof an acid sulfate of a secondary monohydric alcohol having 10 to 20carbon atoms, the secondary monohydric alcohol salt being in the liquidstate, in the presence of a catalytic amount of at least one solidanion-bound metal oxide catalyst. The anion-bound metal oxide catalystis an amorphous or primarily amorphous compound. The molar ratio of theepoxide compound and the secondary monohydric alcohol salt is usuallybetween 3:1 and 1:3.

The invention further involves the composition comprised of (a) a liquidor gaseous epoxide compound having the formula: ##STR7## wherein R₁, R₂,R₃ and R₄ are each H or --(CH₂)_(n) CH₃, and wherein n is 0 to 3, withthe proviso that R₁, R₂, R₃ and R₄ can be the same or different, (b) asodium salt of an acid sulfate of a secondary monohydric alcohol having10 to 20 carbon atoms, the secondary monohydric alcohol salt being inthe liquid state, and (c) a catalytic amount of at least one solidanion-bound metal oxide catalyst. The anion-bound metal oxide catalystis an amorphous or primarily amorphous compound. The molar ratio of theepoxide compound and the secondary monohydric alcohol salt is usuallybetween 3:1 and 1:3.

Another important aspect of the invention is that it encompasses solidanion-bound metal oxide catalysts which are: (a) sulfate-bound tin oxidecatalyst, (b) sulfate-bound nickel oxide catalyst, (c) sulfate-boundaluminum oxide catalyst, (d) sulfate-bound magnesium oxide catalyst, (e)sulfate-bound rubidium oxide catalyst, (f) sulfate-bound thorium oxidecatalyst, (g) sulfate-bound hafnium oxide catalyst, or (h) ananion-bound metal oxide catalyst wherein the anion is SO₄, BF₄, CO₃,HPO₄, SeO₄, MoO₄, B₄ O₇ or PF₆, and the metal oxide is an oxide ofzirconium, nickel, aluminum, tin, magnesium, iron, titanium, thorium,hafnium or rubidium. The anion-bound metal oxide catalyst is anamorphous or primarily amorphous catalyst. The catalysts are useful inthe above-described alkoxylation processes and in the processes set outin the above prior art section.

DETAILED DESCRIPTION OF THE INVENTION

As used herein, all parts, ratios, percentages and proportions are on aweight basis unless otherwise stated herein or otherwise obviousherefrom to one skilled in the art.

The anion-bound metal oxide catalysts of the invention are heterogeneouscatalysts, that is, they are useful in heterogeneous catalysis.Heterogeneous catalysis involves a catalytic reaction in which thereactants and the catalyst comprises two separate phases, e.g., gasesover solids, or liquids containing finely-divided solids as a dispersephase. (By way of contrast, homogeneous catalysis involves a catalyticreaction in which the reactants and the catalyst comprise only onephase, e.g., an acid solution catalyzing other liquid components.) Thesubject alkoxylation reactions of the invention occur on the surface ofthe solid catalyst particles. The individual steps of heterogeneouscatalytic processes probably involve the following:

(1) Diffusion of reactants to surface.

(2) Adsorption of reactants on surface.

(3) Reaction of absorbed reactant to form adsorbed product.

(4) Desorption of product.

(5) Diffusion of product into main stream of a liquid or vapor.

The reaction rates of alkoxylation reactions were unexpectedlysignificantly increased by the solid anion-bound metal oxide catalystsof the invention.

While a catalytic amount of catalyst is to be used, preferably 0.5 to 50weight percent of the catalyst is used based on the total weight of thereactants. Of course, higher levels of the catalyst can be used andmixtures of the catalysts can be used. One or more promoters can also beused.

One of the preferred anion-bound metal oxide catalysts is zirconiumoxysulfate catalyst. It provides a substantial increase of reaction ratein ethoxylations with excellent selectivity. For example, the use ofzirconium oxysulfate catalyst in the ethoxylation of ethylene glycolproduces very little of the undesirable 1,4-dioxane.

Production of the catalyst involves, for example, reacting a compoundhaving an anion with the metal hydroxide, such as, Zr(OH)₄, Zr(OH)₄.xH₂O, Hf(OH)₄, Fe(OH)₃, Al(OH)₃, Th(OH)₄, Ni(OH)₂, and Mg(OH)₂. (Any othersuitable method can be used to prepare the catalyst.)

The metal hydroxide can be produced by hydrolyzing metal oxy-anion groupcompounds, such as, ZrOCl₂.8H₂ O, ZrO(NO)₃)₂.2H₂ O, Zr₅ O₈ (SO₄).xH₂ O,ZrO(C₂ H₃ O₂)₂, ZrOBr₂.xH₂ O, ZrOI₂.8H₂ O, ZrO₅, HfOCl₃.8H₂ O,ZrOOHCl._(n) H₂ O, ZrO(OH)NO₃ and ZrO(SO₄). The hydrolysis can beachieved using a hydrolyzing agent, such as, ammonium hydroxide, sodiumhydroxide, potassium hydroxide, barium hydroxide, lithium hydroxide,magnesium hydroxide, Na₂ SO₄, (NH₄)₂ HPO₄ and so forth. Followinghydrolysis, the solids are removed from the hydrolysis solution, usuallyby filtration, dried (at say 100° C. or any other appropriatetemperatures) and optionally particulated or powdered.

The metal hydroxide is treated with the reactive compound containing ananionic group under suitable conditions. The anion can be monovalent ordivalent or have a higher valence. Examples of the reactive compoundshaving an anionic group are H₂ SO₄, phosphoric acid, nitric acid, etc.Such acids are examples of the reactive compounds having an anionicgroup, but Lewis acids can also be used as such reactive compoundshaving an anionic group. A Lewis acid is a substance that can act as anelectron-pair acceptor. Lewis acids include trivalent derivatives ofboron and aluminum, as well as salts of many other metals. Examples ofspecific Lewis acids are BF₃, BCl₃, AlCl₃, AlF₃, FeCl₃, SnCl₄, ZnCl₂,LiCl, MgCl₂, AlH₃, PF₅, SbF₅ and SO₃.

If one starts with compounds such as ZrOSO₄ and TiOSO₄, thesulfate-bound metal oxide compounds can be prepared directly by addingthe hydrolyzing agent (e.g., sodium hydroxide) to a solution of theZrOSO₄, TiOSO₄ or the like.

The solid anion-bound metal oxide catalyst is normally dried (at 100° C.or any other suitable temperature) before being calcined. The dryingstep to be used is any technique which sufficiently evaporates thevolatile constituents of the impregnating solution.

Calcination of the anion-bound metal oxide catalyst can be done in airor oxygen at a temperature of 300° to 950° C., preferably 500° to 800°C., for a suitable period of time. The calcination is normally conductedfor one to four hours, or more. Zirconium oxysulfate catalyst productionpreferably involves calcination in air at a temperature of about 575° C.

The calcined catalyst has its water molecules removed by thecalcination, so the calcined catalyst should be kept in an air-tightcontainer, such as, a desiccator, until it is used.

The zirconium catalysts of the invention are not zirconyl salts, suchas, zirconium oxysulfate. Instead, the zirconium catalysts of theinvention are anion-bound zirconium oxides. The anion, for example, SO₄,bridges the zirconium oxide moieties. Examples of such anions are SO₄,BF₄, CO₃, BO₃, HPO₄, SeO₄, MoO₄, B₄ O₇ or PF₆, and the metal oxide iszirconium, nickel, aluminum, tin, magnesium, iron, titanium, thorium,hafnium or rubidium. Metal oxides of Group IVB metals are mostpreferred. The anion bound to the metal oxide in the catalysts can beinorganic anions and/or organic anions. Inorganic anionic groups arepreferred, with the sulfate group being the most preferred.

Other anion-bound oxide catalysts can be used in place of anion-boundzirconium oxide catalyst, although the anion-bound zirconium oxidecatalyst is most preferred. Examples of other anion-bound metal oxidesare anion-bound iron oxide (preferred), anion-bound aluminum oxide,anion-bound nickel oxide, anion-bound tin oxide, anion-bound magnesiumoxide, anion-bound rubidium oxide, anion-bound titanium oxide(preferred), anion-bound thorium oxide (most preferred), and anion-boundhafnium oxide (most preferred). Thorium oxide catalysts may be moreadvantageous than zirconium oxide catalysts since they are veryinsoluble and thorium is not amphoteric like zirconium. Amphoteric meansacting as either an acid or base. Experimentation has found thatanion-bound cerium oxide, anion-bound lanthanum oxide, anion-boundtungsten oxide and certain other anion-bound metals do not work ascatalysts in the invention process of catalytically alkoxylating certaincompounds. This lack of catalytic activity of certain anion-bound metaloxides shows the unexpected nature of the invention.

The metal oxides used in the anion-bound metal oxide catalysts areamorphous or used in amorphous form. For example, one uses the amorphousforms of alumina as opposed to the crystalline forms of alumina. Themetal oxides can also be primarily or mainly amorphous, that is, more ofthe metal oxide is in the amorphous state than in the crystalline state.The crystalline forming metal oxides, such as, calcium oxide, are notused.

Only solid, insoluble catalysts are used so that a heterogeneouscatalytic reaction is involved. Catalysts based on K, Ba and Na aresoluble in the reactants and/or product and/or diluent, so they are notused in the invention.

1,4-dioxane or 1,4-diethylene dioxide is undesirable, but is produced toa small extent by all of the invention catalysts. The anion in thecatalyst needs to be bound totally or else it leaches into the reactionmedium and increases the acidity with the resultant production ofdioxane. Preferably 2 to 3 weight percent of the anion (e.g., SO₄) isbound to the metal oxide. The use of Na₂ SO₄ in place of H₂ SO₄eliminates the minor dioxane production caused by the latter, but Na₂SO₄ causes a slower reaction rate. In general, the more basic theanion-bound metal oxide catalyst is, the less the amount of dioxane thatis produced.

The anion-bound metal oxide catalyst is usually used in a finely-dividedparticulate state. Mixtures of anion-bound metal oxide catalysts can beused.

Carriers or supports can be used to support the anion-bound metal oxidecatalyst. The support is used in a particulate form and can be porous ornonporous, although the former is preferred. Usually the supportparticles have diameters between 1 and 5 mm. Preferably, carriers areused which are inert to the reactants and products of the subjectalkoxylation reactions.

The preferred carriers are silica gel and 4 A alumina-silica sieves.Examples of other useful inert carriers are diatomaceous earth, silica,alumina (e.g., α-alumina), silica-alumina, calcined clays, charcoal andzeolites.

The catalysts can even be used in a porous, unsupported form.

The anion-bound metal oxide catalysts can be regenerated or reactivatedby calcination, for example. Zirconium oxysulfate catalyst is preferablyregenerated by calcination in air at a temperature of about 575° C.Generally regeneration calcination is run in air or oxygen at atemperature between 300° and 950° C., preferably between 500° and 800°C., for a period of time which is usually one to four hours, or more.

Generally the recovered catalyst does not have to be regenerated and canbe used as is with no loss of selectivity.

The reactants within the scope of the invention are in the gaseousand/or liquid state, although a reactant could be used in the solidstate if it was in a finely-divided particulate form, for example,suspended in a liquid carrier (diluent) or a different liquid reactant.Solid reactants can also be used if they are dissolved in a liquidsolvent. The anion-bound metal oxide catalyst is used in a solid form.

Examples of liquid nonpolar diluents from which the appropriate diluentcan be selected are: acetic acid nitrile, anthracene, benzene,chlorobenzene, 1,2-dichlorobenzene, ethylbenzene, isopropylbenzene,1-isopropyl-4-methylbenzene, nitrobenzene, propylbenzene,1,3,5-trimethylbenzene, benzoic acid nitrile, perchloro biphenyl,1,3-butadiene, 2-methyl-1,3-butadiene, butane, butanoic acid nitrile,carbon disulfide, carbon tetrachloride, chloroform, cyclohexane, methylcyclohexane, perfluoro cyclohexane, cyclopentane, decalin, decane,ethane, bromoethane, chloroethane, 1,2-dibromoethane,1,1-dichloroethane, difluoro-tetrachloro ethane, nitroethane,pentachloroethane, 1,1,2,2-tetrachloroethane, 1,1,2-trichloro ethane,trichloro-trifluoro ethane, ethylene, perchloroethylene,trichloroethene, heptane, perfluoroheptane, hexane, hexene-1, malonicacid dinitrile, methane, bromomethane, dichloromethane,dichloro-difluoro methane, dichloromethane, nitromethane,tetrachloro-difluoro methane, trichloro-monofluoro methane, naphthalene,nonane, octane, pentane, 1-bromopentane, 1-chloropentane, pentene-1,phenanthrene, propane, 1-bromopropane, 2,2-dimethylpropane,1-nitropropane, 2-nitropropane, propene, 2-methylpropane, propionic acidnitrile, styrene, hydrogenated terphenyl, tetralin toluene and m-xylene.

Examples of liquid moderately polar diluents from which the appropriatediluent can be selected are: acetic acid butyl ester, acetic acid ethylester, acetic acid methyl ester, acetic acid pentyl ester, acetic acidpropyl ester, N,N-diethyl acetic acid amide, N,N-dimethyl acetic acidamide, acrylic acid butyl ester, acrylic acid ethyl ester, acrylic acidmethyl ester, adipic acid dioctyl ester, benzoic acid ethyl ester,benzoic acid methyl ester, 1-iodobutane, carbonic acid ester, vinylchloride, N,N-diethyl formic acid amide, N,N-dimethyl formic acid amide,formic acid ethyl ester, formic acid methyl ester, formic acid2-methylbutyl ester, formic acid propyl ester, furan, furfural, lacticacid butyl ester, lactic acid ethyl ester, methacrylic acid butyl ester,methacrylic acid ethyl ester, methacrylic acid methyl ester, oxalic aciddiethyl ester, oxalic acid dimethyl ester, 1-iodopentane, phosphoricacid triphenyl ester, phosphoric acid tri-2-toly ester, phthalic aciddibutyl ester, phthalic acid diethyl ester, phthalic acid dihexyl ester,phthalic acid dimethyl ester, phthalic acid di-2-methylnonyl ester,phthalic acid dioctyl ester, phthalic acid dipentyl ester, phthalic aciddipropyl ester, propionic acid ethyl ester, propionic acid ethyl ester,propionic acid methyl ester, 1-methyl 2-pyrolidone, sebacic acid dibutylester, sebacic acid dioctyl ester and stearic acid butyl ester.

Examples of liquid hydrogen-bonded diluents from which the appropriatediluent can be selected are: N-ethyl formic acid amide, N-methyl formicacid amide and N-methyl methacrylic acid amide.

Mixtures of inert diluents can be used.

The heterogeneous catalytic reactions of the invention can be effected,for example, in one of three ways: (1) in batch processes; (2) incontinuous fixed-bed processes; and (3) in continuous fluidized reactorprocesses. In a batch reactor, the catalyst is kept suspended in thereactant by shaking or stirring. In a fluidized reactor, the catalyst isat a particular original level. As the velocity of the reactant streamis increased, the catalyst bed expands upward to a second level, and ata critical velocity it enters into violent turbulence. The fluidizedreactor is particularly useful for removing or supplying the heatnecessary to maintain a fixed catalyst temperature. The fluidizedreactor can usually be employed only on a rather large scale since goodfluidization requires a reactor larger than about 1.5 inch in diameter.

The process of the invention broadly involves the liquid or gaseous useof anion-bound metal oxide heterogeneous catalysts for the alkoxylationof active-hydrogen compounds, preferably hydroxyl-containing compounds,such as, primary or secondary alcohols, diols or triols. Mixtures ofactive-hydrogen compounds can be used.

Active-hydrogen organic and inorganic compounds include, for example,hydrogen-containing compounds (ROH, polyols), carboxylic acids (RCO₂ H),thiols (RSH), amines (RNH₂ or R₂ NH), ammonia, water, hydrohalic acids(HX where X is a halogen), alkyl-OCH₂ CH₂ OH, HCN, and bisulfites ofmetals such as alkali and alkaline earth metals. R above is generally asaturated aliphatic hydrocarbon moiety (branched or unbranched alkanes),a saturated monocyclic moiety or an aromatic hydrocarbon moiety (i.e.,an arene moiety). Such organic moieties can be substituted withnonreactive or non-interfering substituents such as halogens, NO₂, etc.The active-hydrogen compounds broadly have the formula HQ (where Q is asaturated or aromatic organic moiety or an inorganic moiety).

The invention can be used to alkoxylate any of the primary or secondarymonohydric alcohols, dihydric alcohols (diols), trihydric alcohols andpolyhydric alcohols (polyols), glycol ethers and alkoxylated ethyleneglycols, all of which are suitable active-hydrogen compounds providedany particular individual compound does not poison the anion-bound metaloxide catalyst. Such hydroxyl-containing compounds can be substitutedwith non-interfering groups, such as, nitro groups, halo groups and thelike.

The monohydric alcohols can be the primary alkyl (monohydric) alcoholshaving 1 to 12 carbon atoms, such as, methanol, ethanol, n-propanol,n-butanol, 1-pentanol, 1-hexanol, 1-heptanol, 1-octanol, 1-decanol,1-dodecanol, isopropanol, isobutanol, 2-methyl-1-butanol,3-methyl-1-butanol, 2-methyl-1-pentanol, 3-methyl-1-pentanol,4-methyl-1-pentanol, 2-ethyl-1-butanol, and 2,4-dimethyl-1-pentanol. Themonohydric alcohols can be the secondary alkyl (monohydric) alcoholshaving 2 to 12 carbon atoms, such as, 2-butanol, 2-pentanol,3-methyl-2-butanol, 2-hexanol, 3-hexanol, 3-methyl-2-pentanol,4-methyl-2-pentanol, 2,4-methyl-3-pentanol, and 2-octanol. Themonohydric alcohols can be paraffinic alcohols (the abovealkyl-alcohols) or olefinic alcohols (e.g., allyl alcohol). Themonohydric alcohols can be alicyclic monohydric alcohols having 3 to 10carbon atoms, such as, cyclohexanol, cycloheptanol, cyclopropanol,cyclobutanol, cyclopentanol and cyclooctanol.

The invention process can be used to alkyoxylate any of the aliphatic,aromatic or heterocyclic compounds containing two hydroxy groups,preferably separated by at least two carbon atoms. The diols can besubstituted if desired with various noninterfering (non-functional)substituents such as ether groups, sulphone groups, tertiary aminegroups, thioether groups, chlorine atoms, bromine atoms, iodine atoms,fluorine atoms, etc. Typical compounds which can be used are listedbelow merely by way of illustration and not limitation: Ethylene glycol,diethylene glycol, 2,2-dimethyl propane-1,3-diol, butane-1,4-diol,hexane-1,6-diol, octane-1,8-diol, decane-1,10-diol, dodecane-1,12-diol,butane-1,2-diol, hexane-1,2-diol, 1-O-methyl glycerol, 2-O-methylglycerol, cyclohexane-1,4-methyl-diol, hydroquinone, resorcinol,catechol, bis(parahydroxyphenyl) butane, 4,4'-dihydroxybenzophenone,napthalene-1,5-diol, biphenyl-4-4'-diol,2,2-bis(3-methyl-4-hydroxyphenyl) propane,2,2-bis(4-hydroxy-dibromophenyl) propane, etc.

Mixtures of different diols can be used. It is also within the purviewof the invention, though less preferred, to use the compounds containingmore than two hydroxy groups, for example, glycerol, diglycerol,hexanetriol, pentaerythritol, etc. Moreover, it is within the scope ofthe invention to utilize the sulfur analogues of the diols. Thus, forexample, instead of using the compounds containing two hydroxy groups,one can use the analogues containing either (a) two --SH groups or (b)one --SH group and one --OH group.

Among the preferred compounds are the aliphatic diols, for example,those of the type:

    HO--(CH.sub.2).sub.n --OH

wherein n has a value from 2 to 12. Another category of aliphatichydroxyl-containing compounds are the polyethylene glycols, i.e.:

    HO--CH.sub.2 --CH.sub.2 --[O--CH.sub.2 --CH.sub.2 ].sub.n --O--CH.sub.2 --CH.sub.2 --OH

wherein n has a value from zero to 10. A category of aromatic diols arethe bisphenols, that is, compounds of the type: ##STR8## wherein R--C--Rrepresents an aliphatic hydrocarbon group containing 1 to 12 carbonatoms and R' represents hydrogen or a lower alkyl radical. In thiscategory are: 2,2-bis(parahydroxyphenyl) propane;2,2-bis(3-isopropyl-4-hydroxyphenyl) propane; and brominated derivativesof bisphenol A, such as, 2,2-bis(4-hydroxy-dibromophenyl) propane.

The alkoxylation of diols can provide dimers or polymers.

The useful trihydric alcohols include glycerol, 1,2,3-butantriol and1,1,1-trihydroxymethylethane. The useful polyhydric alcohols includethose having the formula CH₂ OH(CHOH)_(n) CH₂ OH, wherein n is 2 to 5,such as, arabitol, adonitol, xylitol, mannitol and sorbitol.

Preferably the invention alkoxylation process is used with glycolethers, ethylene glycols (i.e., to produce CARBOWAX®-type products) orTergitol-type products.

CARBOWAX® is the registered trademark of Union Carbide Corporation for aseries of polyethylene glycols. Ethylene glycol can be used to make theCARBOWAX® polyethylene glycols or the CARBOWAX® polyethylene glycols canbe used to make higher molecular weight CARBOWAX® polyethylene glcyols.For example, CARBOWAX® polyethylene glycol 200 can be used to makeCARBOWAX® polyethylene glycol 400. Specifically, the CARBOWAX®polyethylene glycols are liquid and solid polymers of the generalformula H(OCH₂ CH₂)_(n) OH, where n is greater than or equal to 4. Ingeneral, each CARBOWAX® polyethylene glycol is followed by a numberwhich corresponds to its average molecular weight. Generally, theinvention process is not preferred for using CARBOWAX® polyethyleneglycols having an average molecular weight above about 600 to 800 asstarting materials because such CARBOWAX® polyethylene glycols aresolids at room temperature (although they are liquid at the reactiontemperatures, e.g., 110° C.). Examples of useful CARBOWAX® polyethyleneglycols are: CARBOWAX® polyethylene glycol 200, which has an average nvalue of 4 and a molecular weight range of 190 to 210; CARBOWAX®polyethylene glycol 400, which has an average n value between 8.2 and9.1 and a molecular weight range of 380 to 420; and CARBOWAX®polyethylene glycol 600, which has an average n value between 12.5 and13.9 and a molecular weight range of 570 to 630.

The anion-bound zirconium oxide catalyst has a high selectivity toethylene glycol. The reaction temperature is not important and can berun at 50° to 110° C. at a 5:1 weight ratio of H₂ O to ethylene oxideand at various catalyst concentrations greater than 90 percent ofethylene glycol is produced. At a 10:1 weight ratio, greater than 95percent of ethylene glycol is produced.

TERGITOL® is the registered trademark of Union Carbide Corporation for aseries of the sodium salts of the acid sulfate of secondary alcohols of10 to 20 carbon atoms which are nonionic or anionic surfactants.Examples of the TERGITOL® are: TERGITOL® Pentrant 08, which is C₄ H₉CH(C₂ H₅)CH₂ SO₄ --Na; TERGITOL® Pentrant 4, which is C₄ H₉ CH(C₂ H₅)C₂H₄ CH--(SO₄ Na)CH₂ CH(CH₃)₂ ; and TERGITOL® Pentrant 7, which is C₄ H₉CH(C₂ H₅)C₂ H₄ CH--(SO₄ Na)C₂ H₄ CH(C₂ H₅)₂.

Examples of useful glycol ethers are ethylene glycol monoethyl ether,ethylene glycol monobenzyl ether, ethylene glycol monobutyl ether,ethylene glycol monomethyl ether, ethylene glycol monohexyl ether,ethylene glycol monophenyl ether, ethylene glycol monooctyl ether,propylene glycol monomethyl ether and propylene glycol phenyl ether.

The active-hydrogen compound can be a saturated carboxylic acid, HOCOR.The carboxylic acid can be a straight-chain alkanoic acid (C_(n) H_(2n)O, wherein n is 1 to 35), such as, methanoic acid, ethanoic acid,propanoic acid, butanoic acid, pentanoic acid, hexanoic acid, heptanoicacid, octanoic acid, nonanoic acid, decanoic acid, undecanoic acid,dodecanoic acid, tridecanoic acid, tetradecanoic acid, pentadecanoicacid, hexadecanoic acid, heptadecanoic acid, octadecanoic acid,nonadecanoic acid, eicosanoic acid, docosanoic acid, tetracosanoic acid,hexacosanoic acid, octacosanoic acid, triacontanoic acid,tritriacontanoic acid, and pentatriacontanoic acid. The active-hydrogencompound can be a branched alkanoic acid, such as, isopropanoic acid,isobutanoic acid, 2-butanoic acid, 3-methyl-1-butanoic acid,2-methyl-1-butanoic acid, 2-pentaonoic acid, 3-pentanoic acid,2-methyl-1-pentanoic acid, 3-methyl-1-pentanoic acid, 2-ethyl-1-butanoicacid, 2-hexanoic acid, 3-hexanoic acid, 2-methyl-2-pentanoic acid,2,4-dimethyl-3-pentanoic acid and 2-octanoic acid.

The carboxylic acid can be a dienoic acid (C_(n) H_(2n-4) O₂), such as,2,4-pentadienoic acid, 2,4-hexadienoic acid, 2,4-decadienoic acid,2,4-dodecadienoic acid cis-9-, cis-12-octadecadienoic acid, trans-9,trans-12-octadecadienoic acid, and 9,13-docosadienoic acid. Thecarboxylic acid can also be a trienoic acid (C_(n) H_(2n-6) O₂), suchas, 6,10,14-hexadecatrienoic acid, cis-9-, cis-12,cis-15-octadecatrienoic acid, cis-9-, trans-11,trans-13-octadecatrienoic acid trans-9, trans-11,trans-13-octadecatrienoic acid cis-9-, cis-11, trans-13-octadecatrienoicacid, and trans-9, trans-12, trans-15-octadecatrienoic acid. Thecarboxylic acid can further be a tetraneoic acid (C_(n) H_(2n-8) O₂),such as, 4,8,12,15-octadecatetraenoic acid,9,11,13,15-octadecatetraenoic acid, 9,11,13,15-octadecatetraenoic acid,and 5,8,11,14-eicosatetraenoic acid. The carboxylic acid can also be apentaenoic acid (C_(n) H_(2n-10) O₂), such as,4,8,12,15,19-docosapentaenoic acid.

The carboxylic acid can be a substituted, saturated carboxylic acid,such as, iodoacetic acid, o-nitrophenylacetic acid, p-nitrophenylaceticacid, trichloroacetic acid, trifluoroacetic acid, bromoacetic acid,2-bromobutyric acid, 2-bromohexadecanoic acid, 2-bromohexanoic acid,6-bromohexanoic acid, 2-bromo-3-methylbutyric acid,(p-bromophenoxy)acetic acid, 2-bromopropionic acid, 3-bromopropionicacid, 11-bromoundecanoic acid, chloroacetic acid, 3-chlorobutyric acid,3-chloro-2,2-dimethylpropionic acid, (4-chloro-2-methylphenoxy)aceticacid, o-chlorophenoxyacetic acid, p-chlorophenoxyacetic acid,2-(o-chlorophenoxy)propionic acid, p-chlorophenylacetic acid,2-chloropropionic acid, 3-chloropropionic acid, 2,3-dibromopropionicacid, dichloroacetic acid, 2,4-dichlorophenoxyacetic acid,(2,5-dihydroxyphenyl)acetic acid, (3,4-dimethoxyphenyl)acetic acid,2,4-dinitrophenylacetic acid, (2,4-di-tert.-pentylphenoxy)acetic acid,2-(2,4-di-tert.-pentylphenoxy)butyric acid, ethoxyacetic acid,3,11-dihydroxytetradecanoic acid, 2,15,16-trihydroxyhexadecanoic acid,aleoprolic acid and aleprestic acid. Normally, the substituents on anyof the active-hydrogen compounds should be non-interfering, but ifdesired, substituents having active hydrogens, such as, --OH or --SH,can be used (of course, not all --OH and --SH substituents will bereactive).

The active-hydrogen compounds can be a sulfonic acid, RSO₃ H, wherein Ris a univalent organic radical (saturated, alicyclic or aromatic), suchas, the alkanesulfonic acids, for example, methanesulfonic acid,ethanesulfonic acid, propanesulfonic acid, butanesulfonic acid,pentanesulfonic acid and hexanesulfonic acid, alkarenesulfonic acids(R_(n) ARSO₃ H, where R is alkyl and n is 1 to 3), such as,p-toluenesulfonic acid, arenesulfonic acids, such as,2-naphthalenesulfonic acid, 1,3-benzenedisulfonic acid,2,6-naphthalenedisulfonic acid and 1,3,6,8-naphthalenetetrasulfonicacid, fluorinated and chlorofluorinated sulfonic acids, such as, CF₃ SO₃H, ClCF₂ SO₃ H, Cl₂ CFSO₃ H, CHF₂ SO₃ H and ClCHFSO₃ H, othersubstituted sulfonic acids, such as, p-hydroxybenzene sulfonic acid, andother sulfonic acids, such as, methanedisulfonic acid andmethanetrisulfonic acid.

The active-hydrogen compounds can be other sulfur acids where sulfur issubstituted for one or more oxygens in the carboxylic group, such as,methanethiolic acid (HCOSH), methanethionic acid (HCSOH), ethanethionicacid (CH₃ COSH), ethanethionic acid (CH₃ CSOH), methanethionothiolicacid (HCSSH) and ethanethionothiolic acid (CH₃ CSSH).

The active-hydrogen compounds can be alkanethiols (e.g., having 1 to 20carbon atoms), such as, methanethiol, ethanethiol, 2-propanethiol,1-propanethiol, 2-methyl-2-propanethiol, 2-butanethiol,2-methyl-1-propanethiol, 1-butanethiol, 1-pentanethiol, 1-hexanethiol,1-heptanethiol, 1-octanethiol, 1-decanethiol, 1-dodecanethiol,1-hexadecanethiol, 1-octadecanethiol, and cyclohexanethiol, and aromaticthiols, such as, benzene thiol (or phene thiol). Besides monothiols,other thiols can be used such as dithiols, trithiols and tetrathiols(e.g., 1,2-ethanedithiol), and substituted thiols (e.g.,1-amino-2-propane thiol).

Thioglycolic acid and other sulfur analogue acids can be used as theactive-hydrogen compound.

The active-hydrogen compounds can be alkyl-OCH₂ CH₂ OH, such as,Cellosolve™ (C₂ H₅ OCH₂ CH₂ OH), methyl Cellosolve™ and butylCellosolve™.

The active-hydrogen compounds can be bisulfites of metals, such as,NaHSO₃, KHSO₃, LiHSO₃, Mg(HSO₃)₂, Zn(HSO₃)₂ and Be(HSO₃)₂.

The alkoxylating compounds used in the invention alkoxylation processare epoxide compounds having the formula: ##STR9## wherein R₁, R₂, R₃and R₄ are each H or --(CH₂)_(n) CH₃, and wherein n is 0 to 3, with theproviso that R₁, R₂, R₃ and R₄ can be the same or different. The usefulepoxides are basically derivatives of ethylene oxide. Examples of thealkoxylating compound are ethylene oxide, propylene oxide, trimethyleneoxide (2-methyloxirane), isobutylene oxide, 2,2,3-trimethyloxirane,cis-2-butene oxide, trans-2-butene oxide, α-butylene oxide,2,2,3,3,-tetramethyloxirane, 2,3-diethyleneoxirane,2,3-dipropyleneoxirane, 2,3-dibutyleneoxirane, 2-butyleneoxirane,2-isobutyleneoxirane and 2-ethylene-3-propylene oxirane. The preferredalkoxylating agent is ethylene oxide because it is much more reactivethan propylene oxide and the higher members of the subject epoxidecompounds.

A narrow molecular weight range of products is produced with a minimumof undesirable high molecular weight by-products or co-products.

The following examples are illustrative of the invention.

EXAMPLE 1 Preparation Of Sulfate-Bound Zirconium Oxide Catalyst

500 ml. of NH₄ OH (14.8M), 500 ml. of distilled water and 64.5 g ofzirconyl chloride (yellow solid) were combined and the mixture wasplaced in a 2 liter beaker having a watchglass cover. The solution wasstirred for 3 hours. A fine white solid formed quickly as the stirringbegan. The liquid was filtered off in a Buchner funnel. The solidfiltrate was placed in a vacuum oven and dried at 100° C. and 30 inchesof vacuum. After drying in the vacuum oven, about 35 g of white solidwas obtained. The solid was washed in a Buchner funnel using a total of25 ml. of water. The solid was then treated with 1N H₂ SO₄ in the formof an acidic aqueous solution (pH 1). The solid was divided and placedin two Pyrex tubes. The solid was calcined for 3 hours at 600° C. (withair flow). The calcined solid was light yellow and was sulfate-boundzirconium oxide (catalyst). 29.6 g of the catalyst was obtained. The pHof the catalyst in water was acidic.

EXAMPLE 2 Preparation Of CARBOWAX® Polyethylene Glycol 200 UsingSulfate-Bound Zirconium Oxide Catalyst

50.7 g of ethylene glycol and 5.0 g of sulfate-bound zirconium oxidecatalyst (prepared by the method of Example 1) were charged to a Parrbomb. The bomb, three times, was purged with N₂ and evacuated. The bombwas left under 15 pounds per square inch gauge of pressure of N₂. Thebomb was heated and stirred vigorously. Ethylene oxide was added to thebomb based on the following schedule:

                  TABLE I                                                         ______________________________________                                                Reactor      Reactor  Total Ethylene                                  Time,   Temp.,       Pressure,                                                                              Oxide Feed,                                     Mins.   °C.   p.s.i.g. 1                                                                             grams                                           ______________________________________                                        0       84°   18/41    6.0                                             4       96°   24/36    8.1                                             7       86°   24/40    13.2                                            10      81°   24/36    16.1                                            14      79°   24/36    19.8                                            17      81°   24/40    25.7                                            23      78°   24/42    32.1                                            31      82°   24/39    37.1                                            40      79°   24/37    40.6                                            48      81°   26/43    46.2                                            59      84°   27/45    52.2                                            73      82°   29/44    57.6                                            90      81°   30/41    61.1                                            163     84°   29/45    67.2                                            212     84°   30/45    71.9                                            234     104°  33/54    75.3                                            241     93°   34/56    80.2                                            261     99°   36/51    90.0                                            307     97°   38/60    94.2                                            322     98°   41/63    99.6                                            349     97°   42/65    105.1                                           355     96°   57/65    106.9                                           370     97°   52/68    110.8                                           375     97°   62/67    112.8                                           400     98°     54     112.8                                           600     16°     35                                                     ______________________________________                                         Note:                                                                         1. The first number is the pressure before the ethylene oxide addition,       and the second number is the pressure after the ethylene oxide addition. 

An exotherm of 8° to 9° C. occurred immediately after the ethylene oxidewas added to the bomb. The pressure began to quickly drop. Furtherexotherms of 8° to 9° C. occurred after each addition of ethylene oxidethrough the addition totalling 40.6 grams. Then no exotherm was observedin conjunction with ethylene oxide additions until the additiontotalling 67.2 grams. At that an exotherm of 4° to 5° C. occurred. Evenlarger exotherms occurred thereafter at some of the subsequent ethyleneoxide additions. The temperature was raised to 100° C. before theaddition totalling 75.3 grams. The pressure dropped back quickly andcompletely after ethylene oxide additions during the first part of therun, but slowed somewhat later in the run. (The pressure dropped fasterafter reaching 28 p.s.i.g.) Pressure also began building later in therun, but this was partly a function of the increased temperature. (Thepressure rose from 31 p.s.i.g. to 33 p.s.i.g. when the temperature wasraised to 100° C.) After 600 minutes the heat was shut off from thebomb. The product was slightly hazy (possibly due to fine catalystparticles in suspension therein), had a pH of 7 and was slightlyviscous. The product was analyzed using vapor phase chromatography. Theproduct was CARBOWAX® polyethylene glycol 200 produced by theethoxylation of ethylene glycol.

The sulfate-bound zirconium oxide catalyst was recovered using a finesintered glass funnel. The recovered catalyst was washed with ethyleneglycol--the pH at this point of the catalyst in water was neutral. Thecatalyst was then washed with methyl alcohol--the pH was neutral. Thecatalyst was dried in an oven at 130° C.; after 1.5 hours the pH of thecatalyst was 3; and after 3 hours the pH of the catalyst was 3. Therecovered catalyst was then calcined for 1.5 hours at 575° C. with anairflow.

EXAMPLE 3 Preparation of Methyl Cellosolve™ Using Sulfate-BoundZirconium Oxide Catalyst

50.0 g (1.56 moles) of methanol, containing 0.225 percent of water, and1.0 g of sulfate-bound zirconium oxide catalyst (prepared by the methodof Example 1) were charged to a Parr bomb. The bomb was purged with N₂and evacuated three times. The bomb was left under 16 p.s.i.g. of N₂.The bomb was heated and stirred vigorously. Ethylene oxide was added tothe bomb based on the following schedule:

                  TABLE II                                                        ______________________________________                                                 Reactor     Reactor  Total Ethylene                                  Time,    Temp.,      Pressure,                                                                              Oxide Feed,                                     Mins.    °C.  p.s.i.g. grams                                           ______________________________________                                        0        81°  34/38    3.5                                             19       79°  35/35    7.1                                             70       79°  36/46    12.0                                            123      79°  40/47    17.2                                            179      79°    44                                                     overnite 16°    20                                                     ______________________________________                                    

It took 7 minutes for the pressure to reach 36 p.s.i.g. in the bomb, atwhich time the first addition was made. The pressure reached 36 p.s.i.g.at the 45 minute point. The reactants reacted at the moderate rate,i.e., "cooked down" well. After 179 minutes the heat was shut off fromthe bomb. The product was methyl Cellosolve™ produced by theethoxylation of methanol.

EXAMPLE 4

Example 3 was repeated, except that the starting methanol contained0.768 percent of water (water was added). The reaction occurred at aboutthe same rate as in Example 3, but the reaction "cooked down" toslightly lower pressure. The product was methyl Cellosolve™ produced bythe ethoxylation of methanol.

EXAMPLE 5

Example 3 was repeated, except that the starting methanol contained0.0315 percent water. The methanol was dried over activated 4 A sieves.The reaction occurred at about the same rate as and "cooked down"similarly to Example 3. The product was methyl Cellosolve™ produced bythe ethoxylation of methanol.

All of the above water determinations in Examples 3 to 5 were made on aPhotovolt Aquatest IV electronic titrator.

The purpose of Examples 3 to 5 was to determine the effect of watercontent on the preparation of methyl Cellosolve™ using sulfate-boundzirconium oxide catalyst. The reactions in Examples 3 to 5 were run withall of the conditions the same except for the water content of thestarting alcohol. Water did not seem to adversely effect the reactionrate, in fact, a slight increase in activity was observed. Theconversion to product could not be correlated with the water content. Apeak was observed in all of the vapor phase chromatography scans withretention time similar to ethylene glycol, but the area percent of thispeak did not vary significantly between runs.

EXAMPLE 6 Preparation Of CARBOWAX® Polyethylene Glycol UsingSulfate-Bound Zirconium Oxide Catalyst

52.9 g of ethylene glycol and 5.0 g of sulfate-bound zirconium oxidecatalyst was charged to a Parr bomb. The bomb was purged with N₂ andevacuated three times. The bomb was left under 16 p.s.i.g. of N₂. Thebomb was heated to 80° C. and stirred vigorously. Ethylene oxide wasadded to the bomb based on the following schedule:

                  TABLE III                                                       ______________________________________                                                Reactor      Reactor  Total Ethylene                                  Time,   Temp.,       Pressure,                                                                              Oxide Feed,                                     Mins.   °C.   p.s.i.g. grams                                           ______________________________________                                        0       78°   19/40    6.4                                             6       77°   20/40    12.4                                            12      77°   22/44    19.4                                            21      82°   23/44    26.4                                            30      77°   24/43    33.4                                            45      81°   26/46    41.1                                            48      80°     28                                                     ______________________________________                                    

An exotherm of about 30° C. occurred upon the first addition of ethyleneoxide. The ethylene oxide was rapidly consumed. The exotherms becamesmaller on subsequent additions. At the six minute addition, theexotherm went to 99° C. At the 30 minute addition, the exotherm went to84° C. At the 45 minute addition, the exotherm went to 85° C. The rateof ethylene oxide consumption also decreased, and the pressure built upsomewhat in the bomb (possibly due to volume effect). After 48 minutesthe heat was turned off and the catalyst was filtered off from theliquid product. The product was analyzed using vapor phasechromatography. The sample tested contained 0.21 percent of dioxane. Theproduct was clear and colorless and had a neutral pH. The product wasCARBOWAX® polyethylene glycol (viscous liquid polyethylene glycol)prepared by the ethoxylation of ethylene glycol.

EXAMPLE 7 Preparation of CARBOWAX® Polyethylene Glycol UsingSulfate-Bound Zirconium Oxide Catalyst

The filtered sulfate-bound zirconium oxide catalyst (5.0 g) from Example6 was placed in a Parr bomb. The catalyst was not washed, so a smallamount of the liquid product of Example 6 remained in the bomb. 50.7 gof ethylene glycol was charged to the bomb. The bomb was purged with N₂and evacuated three times. The bomb was left under 16 p.s.i.g. of N₂.The bomb was heated and stirred vigorously. Ethylene oxide was added tothe bomb based on the following schedule:

                  TABLE IV                                                        ______________________________________                                                Reactor      Reactor  Total Ethylene                                  Time,   Temp.,       Pressure,                                                                              Oxide Feed,                                     mins.   °C.   p.s.i.g. grams                                           ______________________________________                                        0       81°   19/37    6.2                                             9       79°   22/42    11.9                                            17      77°   24/39    16.5                                            27                     24                                                     ______________________________________                                    

An exotherm to 90° C. occurred upon the first addition of ethyleneoxide. The exotherm was not as great as and the rate of reaction wasslower than the initial reaction in Example 6. At the 9 minute addition,the exotherm went to 88° C. At the 17 minute addition, the exotherm wentto 86° C. The catalyst apparently lost some activity during thereaction. After 27 minutes the heat was turned off and the bomb wasallowed to set at room temperature for about 64 hours. The product wasanalyzed using vapor phase chromatography. The sample tested contained0.29 percent of dioxane. The product was clear and colorless, and had aneutral pH. The product was CARBOWAX® polyethylene glycol prepared bythe ethoxylation of ethylene glycol.

EXAMPLE 8 Preparation of CARBOWAX® Polyethylene Glycol UsingSulfate-Bound Zirconium Oxide Catalyst

42.3 g of ethylene glycol and 4.2 g of sulfate-bound zirconium oxidecatalyst were charged to a Parr bomb. The bomb was purged with N₂ andevacuated three times. The bomb was left under 16 p.s.i.g. of N₂. Thebomb was heated and stirred vigorously. Ethylene oxide was charged tothe bomb based on the following schedule:

                  TABLE V                                                         ______________________________________                                                Reactor      Reactor  Total Ethylene                                  Time,   Temp.,       Pressure,                                                                              Oxide Feed,                                     mins.   °C.   p.s.i.g. grams                                           ______________________________________                                        0       82°   18/41    6.4                                             9       77°   20/41    12.3                                            21      80°   22/46    18.8                                            61      81°     22                                                     ______________________________________                                    

An exotherm went to 99° C. upon the first addition of the ethyleneoxide. The ethylene oxide was consumed fairly rapidly. The secondaddition of ethylene oxide produced only a small exotherm (to 84° C.)and the reaction slowed considerably. At the 21 minute addition, theexotherm went to 82° C. The product was analyzed using vapor phasechromatography, indicating that a substantial amount of product wasproduced. The sample contained 0.12 percent of dioxane. The product wascolorless and slightly hazy (probably due to catalyst in suspension).The product was CARBOWAX® polyethylene glycol prepared by theethoxylation of ethylene glycol.

EXAMPLE 9 Hydrolysis Of Zirconyl Chloride

500 ml. of distilled water and 64.5 g of ZrOCl₂.8H₂ O were placed in abeaker and mixed. 40 ml. of concentrated NH₄ OH solution was added withmixing to the beaker. The pH of the mixture was about 10. 8.4 ml. ofconcentrated HCl solution was added to the admixture to bring the pHback to 7. The admixture was filtered on a M sintered glass funnel. ThepH of the solid filtrate in water was neutral. The solid filtrate wasplaced in a large Soxhlet extractor mounted on a 2 liter flask. Thesolid filtrate was washed with distilled water in the Soxhlet extractor.The liquid mixture was refluxed in the Soxhlet extractor for 13.5 hours.A check of the solid for Cl was essentially negative. The solid wasdried overnight in a vacuum oven at 100° to 110° C. and 30 inches ofvacuum over MgSO₄. The solid was slightly off white and had theconsistency of talcum powder (very fine). The solid was not a hard cakeas had been previously observed in this example. 28.09 g of the solidwere recovered--the solid had a neutral pH in water. The solid wasplaced in 400 ml. of distilled water. Stirring was started and the pHwas 7. After stirring for 2 hours the pH was still neutral. The liquidadmixture was filtered on a C sintered glass funnel. Some of the solidpassed through the filter. The solid filtrate was placed in a vacuumoven at 80° C. and at 30 inches of vacuum over MgSO₄. The filtrate wasdried over a weekend in the vacuum oven (the temperature reached 90°C.). The solid was slightly off-white in color and was a finefree-flowing powder. The pH of the solid in water was neutral; this wasthe first time the pH indicated neutral for Zr(OH)₄. The product waszirconium hydroxide.

EXAMPLE 10 Preparation of Various Anion-Bound Zirconium Oxide Catalysts

Four samples of Zr(OH)₄ (prepared by the method of Example 10) were eachtreated with a different solution, respectively, of NH₄ BF₄, (NH₄)₂HPO₄, (Me₄ N)PF₆ and H₂ SO₄. (Me₄ N)PF₆ istetramethylammoniumhexafluorophosphate. NH₄ BF₄ is ammoniumtetrafluroborate. Reference is made to Table VI below for the treatingagents and other pressing data. Each Zr(OH)₄ sample in the respectivesolution was stirred for 5 to 10 minutes and then filtered on a Buchnerfunnel. Each of the four solids was calcined in a Pyrex tube at 575° C.(with an air flow) for 3 hours.

                                      TABLE VI                                    __________________________________________________________________________    Zr(OH).sub.4                                                                       Treated          pH of                                                                              g.Zr(OH.sub.4 /                                                                      pH in H.sub.2 O                             Sample                                                                             with.sup.1                                                                           In Solution                                                                             Solution                                                                           ml. Soln.                                                                            after calcining                                                                       Notes                               __________________________________________________________________________    First                                                                              NH.sub.4 BF.sub.4                                                                    10.48 g/100 ml H.sub.2 O                                                                4    5 g/78 ml                                                                            3 to 4  off-white after                                                               calcining                           Second                                                                             (NH.sub.4).sub.2 HPO.sub.4                                                           1N(NH.sub.4).sub.2 HPO.sub.4                                                            9    5 g/78 ml                                                                            2 to 3  off-white after                                                               calcining                           Third                                                                              (Me.sub.4 N)PF.sub.6                                                                 21.9 g/100 ml H.sub.2 O                                                                 7    5 g/78 ml                                                                            4       black color                                     insoluluble, added            after calcining-                                more H.sub.2 O, still         probably carbon                                 insoluble                                                         Fourth                                                                             H.sub.2 SO.sub.4                                                                     1N H.sub.2 SO.sub.4                                                                          11.3 g/170 ml                                                                        1 to 2  yellow after                                                                  calcining;                                                                    white after                                                                   cooled                              __________________________________________________________________________     Note: 1. me is methyl                                                    

5 g of the calcined filtrate from the sulfuric acid treated material waswashed overnight with distilled water in a Soxhlet extractor. Thedistilled water after the wash had a pH of 2 to 3 and had a very fine,white, gelatinous solid floating in it. The wash water tested positivefor SO₄ (BaCl₂ test). The solid was removed from the Soxhlet extractor.The solid in water had a pH of 4. The solid was then calcined in a Pyrextube at 575° C. (with an air flow) for 3.5 hours. After calcining thesolid was yellow; upon cooling, the solid turned light yellow. The solidproduct in water had a pH of 2. The product was sulfate-bound zirconiumoxide catalyst.

EXAMPLE 11 Preparation Of CARBOWAX® Polyethylene Glycol UsingPhosphate-Bound Zirconium Oxide Catalyst

42.9 g of ethylene glycol and 4.17 g of zirconium oxy acid phosphatecatalyst (as prepared in Example 10) were charged to a Parr bomb. Thebomb was purged with N₂ and evacuated three times. The bomb was leftunder 16 p.s.i.g. of N₂. The bomb was heated and stirred vigorously.Ethylene oxide was charged to the bomb based on the following schedule:

                                      TABLE VII                                   __________________________________________________________________________               Reactor                                                                            Total Ethylene                                                                        Net                                                   Time,                                                                              Reactor                                                                             Pressure,                                                                          Oxide Feed,                                                                           Feed,                                                                             Exotherm                                          mins.                                                                              Temp., °C.                                                                   p.s.i.g.                                                                           grams   grams.sup.1                                                                       Top Temp., °C.                                                                 Net Temp. Increase,                       __________________________________________________________________________                                        °C.                                0    82°                                                                          19/43                                                                               5.9        112°                                                                           30°                                3    90°                                                                          24/45                                                                              10.9        112°                                                                           22°                                7    83°                                                                          24/45                                                                              16.5        102°                                                                           19°                                12   77°                                                                          24/42                                                                              21.7        90°                                                                            13°                                17   77°                                                                          24/39                                                                              27.3        88°                                                                            12°                                23   78°                                                                          24   --                                                            Reactor                                                                       Restarted                                                                     23   84°                                                                          23/43                                                                              34.2     6.9                                                                              102°                                                                           18°                                28   80°                                                                          26/42                                                                              40.7    13.4                                                                              87°                                                                             7°                                37   79°                                                                          26/45                                                                              47.2    19.9                                                                              92°                                                                            13°                                47   82°                                                                          27/46                                                                              53.9    26.6                                                                              91°                                                                             9°                                53   79°                                                                          28/46                                                                              60.5    33.2                                                                              85°                                        80   82°                                                                          36/50                                                                              68.1    40.8                                                                              84°                                        105  81°                                                                          31/52                                                                              75.8    48.5                                                                              83°                                        __________________________________________________________________________     Note: .sup.1 Net ethylene oxide feed, in grams, after the reactor was         restarted                                                                

Upon first adding ethylene oxide, a 30° C. exotherm occurred.Thereafter, the exotherms decreased. Also, the rate of reaction, whichwas very rapid at first, slowed as the reaction proceeded. During therun, the reaction was stopped after 23 minutes and later started upagain by continued heating and further ethylene oxide additions. Theliquid product was analyzed using vapor phase chromatography. Theproduct contained 0.25 percent of dioxane. The product was clear andpinkish and was a little hazy (probably due to catalyst in suspension).The pinkish color was due to a bad batch of ethylene oxide, which had aslight color and fine particulates in it. The pH of the product wasneutral. The catalyst was filtered off from the liquid product. At thatpoint the pH of the catalyst was 1 to 2. After washing the catalyst withmethanol, the slightly wet catalyst (from methanol) had a pH of 3. Theproduct was CARBOWAX® polyethylene glycol prepared by the ethoxylationof ethylene glycol.

EXAMPLE 12 Ethoxylation Of 1-Butanol Using Sulfate-Bound Zirconium OxideCatalyst

57.9 g of 1-butanol and 4.96 g of sulfate-bound zirconium oxide catalyst(as prepared in Example 10) were charged to a Parr bomb. The pH of themixture was neutral. The bomb was purged with N₂ and evacuated threetimes. The bomb was left under 17 p.s.i.g. of N₂. The bomb was heatedand stirred vigorously. Ethylene oxide was charged to the bomb based onthe following schedule:

                                      TABLE VIII                                  __________________________________________________________________________              Reactor                                                                            Total Ethylene                                                                             Exotherm                                          Time,                                                                             Reactor                                                                             Pressure,                                                                          Oxide Feed,                                                                           Net Feed     Net Temp.                                 mins.                                                                             Temp., °C.                                                                   p.s.i.g.                                                                           grams   grams.sup.1                                                                        Top Temp., °C.                                                                 increase, °C.                      __________________________________________________________________________    0    81°                                                                         21/30                                                                               7.8         103°                                                                           22°                                6    74°                                                                         22/53                                                                              13.5          78°                                                                           4°                                 18  .sup.2                                                                              24                                                                  24  104°                                                                         26                                                                  26  118°                                                                         28/40                                                                              17.9         131°                                                                           13°                                33  113°                                                                         30/43                                                                              22.8         125°                                                                           12°                                40  105°                                                                         30/43                                                                              27.8         113°                                                                           8°                                 48  100°                                                                         30/44                                                                              32.9         105°                                                                           5°                                 56  112°                                                                         38/44                                                                              35.3         114°                                                                           2°                                 73  108°                                                                         33.sup.3                                                            73   17°                                                                         21.sup.4                                                            144 110°                                                                         33/40                                                                              38.6    3.5  115°                                       150 108°                                                                         34/40                                                                              40.8    5.5  111°                                       161 110°                                                                         34                                                                  __________________________________________________________________________     Notes:                                                                        .sup.1 Net etylene oxide fee, in grams, after                                 .sup.2 Temperature was increased to about 100° C.                      .sup.3 The heat was turned off and the sealed bomb stood overnight.           .sup.4 The test was resumed.                                             

Upon first adding ethylene oxide, a 22° C. exotherm occurred with rapidreaction of the ingredients. The second ethylene oxide produced a muchsmaller exotherm and the reaction rate was slower. The temperature wasraised to about 100° C., whereupon the rate of reaction was faster andthe exotherms increased for awhile. After 73 minutes, the heat was shutoff and the sealed bomb was allowed to set overnight. Two more additionsof ethylene oxide were made. The bomb was evacuated before the samplewas taken in order to remove excess ethylene oxide. The product wasanalyzed using vapor phase chromatography and shown to be ethoxylates of1-butanol. It was difficult to determine that dioxane was produced dueto the close proximity of dioxane retention time to that of 1-butanol.The liquid product was fairly clear, and had a slight color due tocatalyst in suspension and from the bad batch of ethylene oxide. The pHof the product was neutral.

EXAMPLE 13 Hydrolysis of Zirconyl Chloride and Treatment With SulfuricAcid.

16 g of ZrOCl₂ 8H₂ O was dissolved in 200 ml. of distilled water in a500 ml. Erlenmeyer flask. 21 g of silica gel and 50 ml. of water (to aidstirring) were added. Enough NH₄ OH was added while stirring to obtain apH of 7. The mixture became very thick as a white gelatinous precipitateformed. The solution was stirred for about one hour. A solid wasfiltered out and dried overnight in a vacuum oven at 80° to 90° C. andunder 30 inches of vacuum over MgSO₄. 29.33 g of silica gel and a finewhite solid was recovered. The material had a pH in water of 3. Thematerial was sieved on a U.S. Pat. No. 8 screen to eliminate thefines--22.10 g of greater than 8 mesh material remained. The silica gelappeared to be coated with white material. The silica gel fizzed andbroke up when placed in water. 22.10 g of the silica gel was treatedwith 166 ml. of 1N H₂ SO₄ and then calcined in Pyrex tubes at 575° C.(with air flow) for 3 hours. The material appeared physically unchangedand still had a "coated" appearance. The pH of the material in water was2 to 3. 20.2 g of the product was obtained. The solid product wassulfate-bound zirconium oxide catalyst bound to silica gel carrier.

EXAMPLE 14 Hydrolysis Of Zirconyl Chloride And Treatment With SulfuricAcid

16 g of ZrOCl₂ 8H₂ O was dissolved in 200 ml. of distilled water in a500 ml. Erlenmeyer flask. 41 g of 4 A sieves and 100 ml. of water (toaid stirring) were added. Enough NH₄ OH was added while stirring toobtain a pH of 7. The mixture became very thick as a white gelatinousprecipitate formed. The solution was stirred for about one hour. A solidwas filtered out and dried overnight in a vacuum oven at 80° to 90° C.and under 30 inches of vacuum over MgSO₄. The material had a neutral pHin water. The material was sieved on a U.S. Pat. No. 20 screen toeliminate the fines--49.49 g of the greater than 20 mesh materialremained. The sieves appeared to have absorbed Zr(OH)₄, a whitepowder--very little fines were present. The sieves appeared to havewhite powder on their surface, but the color was uneven. 10 g. of thesieve material was treated with 75 ml of 1N H₂ SO₄. Some white colorwent into the H₂ SO₄. The H₂ SO₄ -treated sieve material was calcined inPyrex tubes at 575° C. (with air flow) for 3 hours. Some fine particleswere present after calcining. The pH of the sieve material in water was5 to 6. The solid product was sulfate-bound zirconium oxide catalystbound to 4 A sieves.

EXAMPLE 15 Preparation Of CARBOWAX® Polyethylene Glycol Using SilicaGel-Supported Sulfate-Bound Zirconium Oxide Catalyst

155.2 g of ethylene glycol (a syrupy liquid) and 20.2 g of silicagel-supported sulfate-bound zirconium oxide catalyst (as prepared inExample 13) were thoroughly mixed and placed in the reactor tube (oneinch diameter) of a recirculating loop reactor. The reactor tube waspurged with N₂ and evacuated three times. The reactor tube was leftunder 15 p.s.i.g. of N₂. The reactor tube was heated to about 80° C.Ethylene oxide was charged to the reactor tube based on the followingschedule:

    ______________________________________                                                 Reactor     Reactor  Total Ethylene                                  Time,    Temp.,      Pressure,                                                                              Oxide Feed,                                     Mins.    °C..sup.1                                                                          p.s.i.g. grams                                           ______________________________________                                        0        80°/82°                                                                     19/32    5.1                                             5        78°/97°                                                                     22/40    8.1                                             9        75°/98°                                                                     22/40    10.7                                            13       70°/82°                                                                     22/42    12.1                                            18       80°/78°                                                                     22/42    13.4                                            22       78°/73°                                                                     22/43    14.7                                            26       78°/74°                                                                     22/45    16.2                                            31       79°/73°                                                                     22/45    17.4                                            36       72°/70°                                                                     22/45    18.7                                            41       77°/68°                                                                     22/45    20.1                                            46       80°/68°                                                                     22/42    21.5                                            52       85°/67°                                                                     22/52    24.2                                            57       76°/72°                                                                     24/52    29.7                                            63       80°/79°                                                                     24/56    35.6                                            79       78°/76°                                                                     24/55    43.3                                            84       80°/69°                                                                     23/55    50.9                                            92       79°/69°                                                                     24/54    58.6                                            102      83°/76°                                                                     26/55    65.5                                            116      83°/71°                                                                     26/55    72.1                                            127      80°/70°                                                                     25/55    80.3                                            142.sup.2                                                                              81°/69°                                                                     28                                                       142      15°  22                                                       174      85°/60°                                                                     28/58    85.1                                            195      83°/67°                                                                     30/58    90.0                                            199      85°/64°                                                                     30       91.9                                            ______________________________________                                         Note:                                                                         .sup.1 The first number is the temperature of the bomb, and the second        number is the temperature inside of the reactor tube.                         .sup.2 Reactor shut down overnight and then restarted.                   

To samples taken during the run and the final product were analyzed bymeans of vapor phase chromatography. The product had a pH in water ofneutral. The catalyst was washed with methanol to remove color caused byethylene oxide. The product was CARBOWAX® polyethylene glycol producedby ethoxylation of ethylene glycol.

EXAMPLE 16 Preparation Of Sulfate-Bound Zirconium Oxide Catalyst

10 g of Zr(OH)₄ and 150 ml. of 0.5N H₂ SO₄ were placed in a beaker andstirred for a few minutes. The solid was filtered off from the solution.The solid was calcined in a Pyrex tube at 575° C. (with air flow) for33/4 hours. The calcined solid was white and had a pH in water of 1. Thesolid was stored in a desiccator until needed. The product wassulfate-bound zirconium oxide catalyst.

EXAMPLE 17 Ethoxylation Of 2-Octanol Using Sulfate-Bound Zirconium OxideCatalyst

49.9 g of 2-octanol and 3.0 g of sulfate-bound zirconium oxyide catalyst(as prepared by the method of Example 16) were charged to a Parr bomb.The bomb was purged with N₂ and evacuated three times. The bomb was leftunder 15 p.s.i.g. of N₂. The bomb was heated and stirred vigorously.Ethylene oxide was added to the bomb based on the following schedule:

                  TABLE X                                                         ______________________________________                                                Reactor      Reactor  Total Ethylene                                  Time    temp.,       Pressure,                                                                              Oxide Feed,                                     Mins.   °C.   p.s.i.g. grams                                           ______________________________________                                        0        82°  18/36     6.6                                            7       .sup.1       30                                                       11      115°  31/54    11.4                                            19      112°  31.58    17.0                                            44      108°  33/52    20.2                                            52      107°  48.49    20.5                                            113     107°  26       20.5                                            ______________________________________                                         Note: .sup.1 The reactor temperature was increased to 100° C.     

Immediately after the ethylene oxide was added to the bomb an exothermto 85° C. occurred. At the 7 minute point in the run, the temperature ofthe reactor was increased to 110° C. and the reactor pressure rose to 31p.s.i.g. When ethylene oxide was added at the 11 minute point in therun, an exotherm to 125° C. occurred. No noticeable exotherms occurredthereafter during the run. The product was analyzed using vapor phasechromatography. The product had a neutral pH in water.

The product was ethoxylates of 2-octanol.

EXAMPLE 18 Preparation Of Sulfate-Bound Zirconium Oxide

50 g of commercial Zr(OH)₄ (slightly damp, file white powder, with NH₃odor) was washed free of NH₃ with distilled H₂ O. After the 750 ml.washing, the pH was neutral. The powder was washed with an additional250 ml. of distilled H₂ O. The pH was still neutral. A check of the washwater for Cl was negative (AgNO₃ test). The powder was dried overnightin oven at 100° C. in an open beaker. 29.61 g of fine white powder wasremoved after drying. No NH₃ odor was evident. The pH of the solid in H₂O was neutral.

10 grams of the treated Zr(OH)₄ was treated with 150 ml. of 1NH₂ SO₄ ina beaker with stirring for 5 to 10 minutes. The solution was filtered onNo. 42 filter paper. The solid filtrate was dried for 2.5 hours in anopen beaker in a 100° C. oven. The pH of the filtrate in water was 3.The solid was calcined in a Pyrex tube at 575° C. (with air flow) for23/4 hours. The pH of the calcined solid in water was 0 to 1. One literof distilled water and the solid were stirred overnight in a beaker atroom temperature. The slid was filtered off. The solid filtrate wascalcined in a Pyrex tube at 575° C. (with air flow) for 3.5 hours. Thecalcined solid was white and had a pH in water of 1 to 2. The productwas sulfate-bound zirconium oxide catalyst.

EXAMPLE 19 Preparation Of Phosphate-Bound Zirconium Oxide Catalyst

10 grams of the treated Zr(OH)₄ (prepared by the method of Example 18)was treated with 150 ml. of 1N (NH₄)₂ HPO₄ solution in a beaker withstirring for 5 to 10 minutes. The solution was filtered on No. 42 filterpaper. The solid filtrate was dried for 2.5 hours in an open beaker in a100° C. oven. The pH of the filtrate in water was 8. The solid wascalcined in a Pyrex tube at 575° C. (with air flow) for 23/4 hours. ThepH of the calcined solid in water was 2. One liter of distilled waterand the solid were stirred overnight in a beaker at room temperature.The solid was filtered off. The solid filtrate was calcined in a No. 5Pyrex tube at 575° C. (with air flow) for 3.5 hours. The calcined solidwas light yellow and had a pH in water of 3 to 4 . The zirconiumoxy-anion product was phosphate-bound zirconium oxide catalyst.

EXAMPLE 20 Preparation Of Fluoride-Bound Zirconium Oxide Catalyst

9.61 grams of the treated Zr(OH)₄ was treated with 150 ml. of 1N HFsolution in a beaker with stirring for 5 to 10 minutes. The solution wasfiltered on No. 42 filter paper. The solid filtrate was dried for 2.5hours in an open beaker in a 100° C. oven. The pH of the filtrate inwater was 4. The solid was calcined in a Pyrex tube at 575° C. (with airflow) for 23/4 hours. One liter of distilled water and the solid werestirred overnight in a beaker at room temperature. The solid wasfiltered off. The solid filtrate was calcined in a Pyrex tube at 575° C.(with air flow) for 3.5 hours. The calcined solid was pinkish and had apH in water of 4, and was stored in a desiccator until needed. Theproduct was fluoride-bound zirconium oxide catalyst.

EXAMPLE 21 Preparation Of CARBOWAX® Polyethylene Glycol UsingPhosphate-Bound Zirconium Oxide Catalyst

51.3 g of ethylene glycol and 5.0 g of phosphate-bound zirconium oxidecatalyst (prepared by the method of Example 19) were charged to a Parrbomb. The pH of the mixture was 5. (The pH of ethylene glycol by itselfwas 6.) The following formula was used to determine the amount ofethylene oxide needed: ##EQU1## The bomb was purged with N₂ andevacuated three times. The bomb was left under 16 p.s.i.g. of N₂. Thebomb was heated to 80° C. and stirred vigorously. Ethylene oxide wascharged to the bomb based on the following schedule:

                  TABLE XI                                                        ______________________________________                                                Reactor      Reactor  Total Ethylene                                  Time,   Temp.,       Pressure,                                                                              Feed,                                           Mins.   °C.   p.s.i.g. Grams                                           ______________________________________                                        0       77°   19/28    38                                              5       79°   23/38    8.2                                             8       88°   32/45    12.2                                            9       91°   40/47    14.3                                            10      91°   40/47    16.1                                            12      89°   40/47    18.1                                            14      86°   40/46    19.6                                            16      82°   40/46    21.7                                            17      78°   40/46    23.5                                            20      83°   40/46    24.9                                            23      82°   40/46    26.8                                            25      78°   40/46    28.1                                            28      83°   40       40.1.sup.3                                      59      83°   43       .sup.3                                          59      81°   26/44    46.1                                            61      83°   40/50    50.0.sup.3                                      76      .sup.2       44                                                       81      126°  40/57    51.9                                            84      130°  40       .sup.3                                          246     122°  54       97.0                                            314     122°  51/56    97.8                                            324     121°  51/58    98.7                                            338     121°  51/64    99.7                                            356     122°  52       100.8                                           364     122°  52/72    102.4                                           378     122°  54/72    103.7                                           394     121°  54/72    104.6                                           414     122°  54/72    107.0                                           438     122°  54/64    105.0                                           439     121°  55/76    109.4                                           454     121°  56/74    112.3                                           484     121°  56/80    114.7                                           504     121°  60                                                       .sup.4  17°   38                                                       ______________________________________                                         Note:                                                                         .sup.1 Turned off reactor heat and restarted the next day.                    .sup.2 The reactor temperature was increased to 125° C.                .sup.3 Constant feed of ethylene oxide to the reactor and then the            periodic addition was resumed as indicated.                                   .sup.4 The reaction heat was cut and the ingredients were allowed to set      overnight in the sealed bomb.                                            

The reaction proceeded rapidly and an exotherm of 4° to 10° C. wasobserved on the first few additions. The rate of reaction slowedsomewhat as ethylene oxide was added, but still was fairly rapid; andpressure built up somewhat (some due to volume effect). The bomb wasallowed to set overnight at room temperature after 40.1 g of ethyleneoxide had been added. The reaction was started at about 120° C. thefollowing morning, and exotherm again was observed, as well as goodactivity. (A slow constant feed was tried at a couple points during thereaction with good results--fairly stable pressure.) The pressure builtup eventually, so the constant feed was stopped (ethylene oxide was notconsumed rapidly enough). Addition of ethylene oxide was difficult atthe end of reaction due to high reactor pressure (higher than the feed).The liquid product was clear and colorless, and had a pH of 6. Thecatalyst was filtered out using No. 1 filter paper and then an Fsintered glass funnel. The product was analyzed using vapor phasechromatography. The catalyst was rinsed out of the bottom of the bombwith about 100 ml. of distilled water. The pH of the wash water was 6and the pH of the catalyst was 5. The catalyst was light brown. Thecatalyst was calcined in a Pyrex tube at 575° C. (with air flow) for 1hour and then stored in a desiccator. The pH of the calcined catalyst inwater was 2 to 3. The product was CARBOWAX® polyethylene glycol 200prepared by the ethoxylation of ethylene glycol.

EXAMPLE 22 Preparation Of CARBOWAX® Polyethylene Glycol 200 UsingPhosphate-Bound Zirconium Oxide Catalyst

50.8 g of ethylene glycol and 4.56 g of phosphate-bound zirconium oxidecatalyst (which had been recovered and recalcined in Example 20) werecharged to a Parr bomb. The pH of the mixture was 5. (The pH of ethyleneglycol by itself was 6.) The following calculation determined the amountof ethylene oxide needed: ##EQU2##

The bomb was purged with N₂ and evacuated three times.

The bomb was left under 16 p.s.i.g. of N₂. The bomb was heated to 120°C., stirred vigorously. Ethylene oxide was charged to the bomb based onthe following schedule:

                  TABLE XII                                                       ______________________________________                                                         Reactor   Total    Top Of                                    Time, Reactor    Pressure, Oxide Feed,                                                                            Exotherm,                                 Mins. Temp., °C.                                                                        p.s.i.g.  grams    °C.                                ______________________________________                                        0     126°                                                                              24/54     5.4      135° C.                            5     120°                                                                              26/58     9.8      131°                               9     121°                                                                              28/58     13.6     130°                               13    121°                                                                              28/60     18.0     131°                               18    120°                                                                              28/60     21.5     130°                               24    119°                                                                              29/60     24.8     132°                               30    121°                                                                              30/62     27.6     129°                               34    120°                                                                              31/60     30.1     125°                               38    120°                                                                              32/64     32.7     126°                               43    19° 32.sup.1                                                     136   121°                                                                              56.sup.2  77.4                                               225   120°                                                                              46.sup.3                                                     267   121°                                                                              56        84.0                                               282   120°                                                                              49/56     85.0                                               305   120°                                                                              49/60     86.1                                               312   120°                                                                              51/62     87.4                                               318   120°                                                                              54/66     88.3                                               332   120°                                                                              50/68     89.5                                               355   121°                                                                              50/62     90.8                                               367   120°                                                                              51/66     92.2                                               373   120°                                                                              55/66     93.1                                               403   120°                                                                              52/65     94.1                                               415   121°                                                                              52/66     95.3                                               420   120°                                                                              55/66     95.8                                               445   120°                                                                              52.sup.4                                                     445   18° 36.sup.5                                                     447   128°                                                                              51/60     99.5                                               448.sup.6                                                                           121°                                                                              54/60     99.7                                               ______________________________________                                         Notes:                                                                         .sup.1 Started constant feed of ethylene oxide.                              .sup.2 Stopped constant feed of ethylene oxide.                               .sup.3 Resumed making ethylene oxide additions.                               .sup.4 Shut off reactor heat and allowed to set overnight.                    .sup.5 Resumed heating reactor.                                               .sup.6 Run was shut down shortly thereafter.                             

The reaction was started at about 120° C. An exotherm was observed whenethylene oxide was added and the reaction rate was readily comparable toExample 21.

Exotherms continued for several additions of ethylene oxide. After 38minutes of the run, a constant feeding of ethylene oxide at a rate of 1g per 1.5 minutes was conducted. The reactor pressure at the start ofthe constant feed was 43 p.s.i. The reaction slowed as the totalethylene oxide feed approached 80 g. The feed rate had to be slowed asthe pressure built up. The same happening had been observed in Example21. It was not clear whether the slow down of the activity was due tocatalyst inactivity, dilution effect (increased volume of liquid vs.fixed amount of catalyst), or high bomb pressure. The liquid product wasclear and colorless and had a pH of 6. The liquid product was pouredfrom the bomb. The product was analyzed using vapor phasechromatography. CARBOWAX® polyethylene glycol 200 was not quite producedbecause not quite enough ethylene oxide was added. The purpose of thisexample is to see if the recovered and recalcined catalyst could be usedto produce CARBOWAX® ethylene glycol 200.

EXAMPLE 23 Preparation Of CARBOWAX® Polyethylene Glycol 400 UsingSulfate-Bound Zirconium Oxide Catalyst

42.0 g of CARBOWAX® polyethylene glycol 200 and 3.81 g of sulfate-boundzirconium oxide catalyst were charged to a Parr bomb. The bomb waspurged with N₂ and evacuated three times. The bomb was left under 16p.s.i.g. of N₂. The bomb was heated to 65° C. and stirred vigorously.The catalyst used in this reaction was less acidic than others used insome of these examples. Also the starting reaction was a lowertemperature to try to eliminate high exotherms and possible colorproblems. Ethylene oxide was charged to the bomb based on the followingschedule:

                  TABLE XIII                                                      ______________________________________                                                             Reactor  Total Ethylene                                  Time,   Reactor      Pressure,                                                                              Oxide Feed,                                     Mins.   Temp., °C.                                                                          p.s.i.g. grams                                           ______________________________________                                         0       65°  19/37    6.3                                              8       65°  32/43    9.9                                              18      62°  40 (1)                                                    37     129°  34/50    12.5                                             43     118°  36/52    15.2                                             54     120°  36/52    18.0                                             61     119°  36/53    20.4                                             69     120°  38/55    22.9                                             80     120°  39/55    23.0                                             89     120°  39/56    27.4                                            100     120°  40 (2)                                                   100      18°  19 (3)                                                   116      65°  22/35    32.8                                            121     55           34                                                       138     129°  52 (4)                                                   145     122°  40/58    34.2                                            151     124°  40/58    35.9                                            155     131°  40/58    37.7                                            172     125°  40/70    39.4                                            183     121°  38/68    40.8                                            193     124°  40/58    42.0                                            230     123°  36 (5)                                                   260      31°  22                                                       ______________________________________                                         Notes:                                                                        (1) Reactor temperature was raised to about 120° C.                    (2) Reactor was shut down overnight.                                          (3) Reactor was restarted.                                                    (4) Temperature was raised to about 120° C.                            (5) The heat was turned off.                                             

There was very little exotherm on the initial ethylene oxide addition.Also, the reaction was slow at 65° C., so the temperature was raised toabout 120° C. The reaction rate was much faster, but still no exothermwas observed when ethylene oxide was added. The reaction was stoppedovernight. At that point, the liquid product was clear and colorless,and had a pH of 6. The reaction restarted at 65° C. to try to avoid hightemperature operation and possible decomposition. After adding a smallamount of ethylene oxide, the temperature was raised to about 120° C.(At one point in the run, the temperature reached 135° to 136° C. forabout 5 minutes.) After the initial slight exotherm, no furtherexotherms were detected. The reaction was slow toward the end. Thereaction was stopped and the gaseous ethylene oxide was removed. Theliquid product was light yellow and had a pH of 6. The (pinkish brown)catalyst was filtered off. The catalyst was washed with 150 ml ofdistilled water, which resulted in a white catalyst. The pH of the waterwas 3 to 4 and of the catalyst in the water was 3. The catalyst waslight yellow in water and was white when dry. The molecular weight ofthe product was too high and possibly the gas chromatography columnmight be plugged, so no vapor phase chromatography analysis was made.The catalyst was calcined in a Pyrex tube at 575° C. (with air flow) for3.5 hours.

EXAMPLE 24 Hydrolysis Of Ethylene Oxide Using Sulfate-Bound ZirconiumOxide Catalyst

40.0 g of water and 3.30 g of sulfate-bound zirconium oxide catalyst(the recovered, recalcined catalyst from Example 23) were charged to aParr bomb. The bomb was purged with N₂ and evacuated three times. Thebomb was left under 16 p.s.i.g. of N₂. The bomb was hated to about 80°C. and stirred vigorously. Ethylene oxide was charged to the bomb basedon the following schedule:

                  TABLE XIV                                                       ______________________________________                                                             Reactor  Total Ethylene                                  Time,   Reactor      Pressure Oxide Feed,                                     Mins.   Temp., °C.                                                                          p.s.i.g. grams                                           ______________________________________                                         0       78°  22/38    3.3                                             10       79°  31/42    6.0                                             24       78°  26/43    9.3                                             35       79°  29/44    13.4                                            55       79°  26 (1)                                                            18°  17 (2)                                                   55      102°  30/54    17.6                                            58      100°  34/50    19.9                                            62      105°  38/58    21.6                                            64      106°  38/56    23.1                                            66      105°  38/58    24.1                                            68      104°  38/54    26.6                                            72      103°  38/58    28.2                                            74      104°  38/56    30.1                                            78      103°  38/58    32.0                                            82      105°  38/58    34.0                                            85      102°  38/58    35.5                                            88      101°  38/58    37.0                                            91       99°  38/59    38.9                                            94      100°  38/59    41.2                                            99      100°  38/59    43.2                                            103      99°  38/59    45.3                                            105      99°  38/58    46.9                                            109      99°  38/59    49.0                                            ______________________________________                                         Notes                                                                         (1) Heat was turned off overnight.                                            (2) Heat was applied again next day.                                     

No exotherms were observed until the temperature was raised to about100° C. Small exotherms (2° to 5° C.) were observed thereafter whenethylene oxide was added. The rate of reaction was faster at 100° C.,and remained fairly fast throughout the reaction. The reaction wasstopped, the bomb was evacuated and the catalyst was filtered out. Theliquid product was clear and colorless, although some of the catalystremained in the product. The product had a pH of 4 to 5. 25.56 g ofwater was removed from the product on a Rotavapor at 90° C. and 30inches of vacuum. 20.54 g of product remained as a kettle product. 75 mlof ethyl acetate was added to the kettle product in a separation funnelbut layers were evident. The material was removed and dried overanhydrous MgSO₄ (no clumping was observed). The solution was filteredand the ethyl acetate was removed in vacuo from the solid filtrate. Thesolid product was analyzed using vapor phase chromatography. The productwas hydrolyzed ethylene oxide (ethylene glycol, diethylene glycol, andtriethylene glycol).

EXAMPLE 25 Ethoxylation Of 1-Butanol Using Sulfate-Bound Zirconium OxideCatalyst

74.1 g (1 mole) of 1-butanol nd 3.30 g of sulfate-bound zirconium oxidecatalyst were charged to a Parr bomb. (The catalyst had been prepared bythe procedure of Example 1.) The bomb was purged with N₂ and evacuatedthree times. The bomb was left under 16 p.s.i.g. of N₂. The bomb washeated to about 100° C. and stirred vigorously. The pH of the materialin the bomb was 6. Ethylene oxide was charged to the bomb based on thefollowing schedule:

                  TABLE XV                                                        ______________________________________                                                             Reactor  Total Ethylene                                  Time,   Reactor      Pressure Oxide Feed,                                     Mins.   Temp., °C.                                                                          p.s.i.g. grams                                           ______________________________________                                         0      112°  24/33    5.5                                             17      110°  33/42    8.7                                             33      109°  34/42    11.0                                            136     109°  27                                                       ______________________________________                                    

Once ethylene oxide was added, the reaction proceeded slowly. Thereaction was kept at 109° C. for two hours after the last ethylene oxideaddition, and then the reactor system was shut down. A total of 11 gramsof ethylene oxide were used, so the molar ratio of 1-butanol to ethyleneoxide was 4 to 1. The product was clear and colorless and had a pH of 6.The catalyst was filtered off. The catalyst was placed in a Pyrex tubeand calcined at 575° C. (with air flow) for 3.5 hours. The pH of thecatalyst in water was neutral. The product was ethoxylates of 1-butanol.

EXAMPLE 26 Ethoxylation Of 1-Butanol Using Sulfate-Bound Zirconium OxideCatalyst

74.1 g (1 mole) of 1-butanol and 5.20 g of sulfate-bound zirconium oxidecatalyst (which had been recovered and recalcined in Example 25) werecharged to a Parr bomb. The bomb was purged with N₂ and evacuated threetimes. The bomb was left under 16 p.s.i.g. of N₂. The bomb was heated to80° C. and stirred vigorously. The pH of the material in the bomb was 6.Ethylene oxide was charged to the bomb based on the following schedule:

                  TABLE XVI                                                       ______________________________________                                                             Reactor  Total Ethylene                                  Time,   Reactor      Pressure Oxide Feed,                                     Mins.   Temp., °C.                                                                          p.s.i.g. grams                                           ______________________________________                                         0       81°  19/33    6.6                                              7       (1)         32                                                       10      110°  40/45    9.8                                             15      108°  40/46    11.1                                            80                   29                                                       ______________________________________                                         Note:                                                                         (1) Raised temperature of the reactor.                                   

Once ethylene oxide was added, the reaction proceeded slowly and noexotherm was noticed. So the temperature was raised to 110° C. and thereaction rate increased. No exotherms were noticed at the highertemperature level. The reactor system was shut down. A total of 11.1 gof ethylene oxide were used, so the molar ratio of 1-butanol to ethyleneoxide was 4 to 1. The liquid product was clear and colorless and had apH of 6. The catalyst was filtered off. The product was analyzed byvapor phase chromatography. The excess catalyst was rinsed (but notwashed) from the bomb using acetone. The catalyst was calcined in aPyrex tube at 575° C. (with air flow) for 3 hours. The pH of thecalcined catalyst was neutral. The product was ethoxylates of 1-butanol.

EXAMPLE 27 Ethoxylation Of Glycerol Using Sulfate-Bound Zirconium OxideCatalyst

60.2 g of anhydrous glycerol and 3.0 g of sulfate-bound zirconium oxidecatalyst were charged to a Parr bomb. (The catalyst had been prepared bythe procedure of Example 1.) The bomb was purged with N₂ and evacuatedthree times. The bomb was left under 16 p.s.i.g. of N₂. The bomb washeated to 80° C. and stirred vigorously. The pH of the material in thebomb was 5 to 6. Ethylene oxide was charged to the bomb based on thefollowing schedule:

                  TABLE XVII                                                      ______________________________________                                                         Reactor  Total Ethylene                                                                          Top Of                                    Time, Reactor    Pressure,                                                                              Oxide Feed,                                                                             Exotherm,                                 Mins. Temp., °C.                                                                        p.s.i.g. grams     °C.                                ______________________________________                                         0    81° 18/57    3.4       86°                                 6    80° 36/58    6.7       86°                                13    79° 42/56    9.3       86°                                15    78° 44/56    11.7      87°                                26    78° 42/56    14.2      89°                                35    80° 40/54    17.3      83°                                40    82° 44/54    19.6                                                59    80° 29/47    22.0                                                107   81° 24                                                           ______________________________________                                    

A small exotherm (about 6° C.) was observed for the first few additionsof ethylene oxide. The reaction rate was slower than with ethyleneglycol, but it still was fairly fast. The liquid product was clear andcolorless, and had a pH of 5. The catalyst was filtered off, but thefiltration was very difficult because the liquid product was very thick(viscous). The product was analyzed by vapor phase chromatography. Thecatalyst was washed with about 200 ml of distilled water and placed in atest tube. The product was ethoxylated glycerol.

EXAMPLE 28 Ethoxylation Of 1-Butanol Using Sulfate-Bound Zirconium OxideCatalyst

74.1 g (1 mole) of 1-butanol and 3.0 g of sulfate-bound zirconium oxidecatalyst were charged to a Parr bomb. (The catalyst had been prepared byprocedure of Example 1.) The bomb was purged with N₂ and evacuated threetimes. The bomb was left under 16 p.s.i.g. of N₂. The bomb was heated to110° C. and stirred vigorously. The pH of the material in the bomb was 5to 6. Ethylene oxide was charged to the bomb based on the followingschedule:

                  TABLE XVIII                                                     ______________________________________                                                             Reactor  Total Ethylene                                  Time,   Reactor      Pressure,                                                                              Oxide Pressure,                                 Mins.   Temp., °C.                                                                          p.s.i.g. grams                                           ______________________________________                                         0      110°  22/32    5.3                                             15      110°  32/40    8.4                                             31      109°  33/42    11.2                                            50      109°  27                                                       ______________________________________                                    

The reaction rate was fairly slow but was comparable with other1-butanol runs. The reactor was shut down, and the catalyst was filteredout of the liquid product. 79.52 g of the liquid product was obtained. Atotal of 11.2 g of ethylene oxide was used, so the molar ratio of1-butanol to ethylene oxide was 4 to 1. The liquid product was clear andcolorless and had a pH of 5 to 6. The liquid product was analyzed byvapor phase chromatography.

40 g of the liquid product was distilled in the fractionating columnhaving a small condensor. The fractions of the distillation were:

                  TABLE XIX                                                       ______________________________________                                                                       Percent                                        Fraction   Temp., °C.                                                                         Wt. g.  Of Total Product                               ______________________________________                                        1-Butanol  117° 27.39   69.4                                           Butyl      171° 7.46    18.9                                           Cellosolve™                                                                Kettle                 4.61    11.7                                           Product                                                                       (higher                                                                       ethoxylates)                                                                  Total                  39.46   100                                            ______________________________________                                    

28.71 g of the liquid product was separated into 1-butanol and butylcellosolve on a Rotavapor. (conditions: 60° C. on water bath, vacuumpump on condensor). The fractions were:

                  TABLE XX                                                        ______________________________________                                                                Percent                                               Receiver        Wt., g.sup.1                                                                          Of Total Product                                      ______________________________________                                        Butanol         16.90   65.5                                                  Kettle Product  8.92    34.5                                                  Butyl Cellosolve™                                                          Higher Ethoxylates                                                            Total           25.82   100                                                   ______________________________________                                         Note:                                                                         .sup.1 Probably lost some product to the vacuum.                         

EXAMPLE 29 Calcining Commercial Zirconium Sulfate Oxide

Commercial zirconium sulfate oxide was placed in a Pyrex tube andcalcined at 800° C. (with air flow) for 23/4 hours. The pH of thecatalyst after calcining was 2. The calcined catalyst was insoluble inwater.

EXAMPLE 30 Preparation Of CARBOWAX® Polyethylene Glycol Using CalcinedCommercial Zirconium Sulfate Oxide

40.0 g of ethylene glycol and 2.5 g of the calcined commercial zirconiumsulfate oxide from Example 29 were charged to a Parr bomb. The formulafor commercial zirconium sulfate oxide is ZrO(SO₄).H₂ SO₄.3H₂ O. Thebomb was purged with N₂ and evacuated three times. The bomb was leftunder 16 p.s.i.g. of N₂. The bomb was heated to 80° C. and stirredvigorously. The pH of the material in the bomb was 5. Ethylene oxide wascharged to the bomb based on the following schedule:

                  TABLE XXI                                                       ______________________________________                                                         Reactor  Total Ethylene                                                                          Top Of                                    Time, Reactor    Pressure,                                                                              Oxide Feed,                                                                             Exotherm,                                 Mins. Temp., °C.                                                                        p.s.i.g. grams     °C.                                ______________________________________                                         0    79° 18/32    5.0       91°                                 7    83° 24/44    11.4      106°                               11    79° 25/40    16.3      87°                                18    82° 30/46    22.1       (1)                                      27    81° 28/46    29.5                                                66    80° 24/44    35.2      85°                                76    83° 38/54    40.0                                                109   83° 38                                                           ______________________________________                                         Note:                                                                         (1) No exotherm was noticed.                                             

Exotherms were observed upon the first few additions of ethylene oxide.The reaction rate was slower than the sulfate-bound zirconium oxidecatalysts prepared in the above examples, but it was still fairly fast.The reactor was shut down and the catalyst was filtered from the liquidproduct. The liquid product was clear and colorless, and had a pH of 5to 6. The product was analyzed by vapor phase chromatography. Catalystwas rinsed from the bomb. The catalyst was calcined in a Pyrex tube at575° C. (with air flow) for 1 hour. 2.05 g of catalyst was recovered.The pH of the catalyst in water was about 6. The product was CARBOWAX®polyethylene glycol prepared by the ethoxylation of ethylene glycol.

EXAMPLE 31 Preparation of Sulfuric Acid-Treated Zirsil 401 Catalyst

Zirsil 401 (from Magnesium Elektron, Inc.) was dried at 100° C. in anopen beaker over a weekend. 25 g. of the dried white powder was treatedwith 375 ml. of 1NH₂ SO₄ in a beaker with stirring for about 5 minutes.The admixture was filtered. The solid filtrate was dried at 100° for 1.5hours. The solid was calcined in Pyrex tubes at 575° C. (with air flow)for 2 hours. Zirisil 401 is a composition which includes 52 percent ofsilicon oxide, 16 percent of hydrous zirconium oxide, 12 percent ofzircon, 2 to 3 percent of sodium iron at 120 ppm and titanium at 150ppm, which has an ignition loss at 1000° C. for one hour of 20 percent(mostly water), and which has a free moisture at 150° C. for 15 minutesof 12 percent.

EXAMPLE 32 Preparation Of Basic Sulfate-Bound Zirconium Oxide Catalyst

35.0 g of basic sulfate-bound zirconium oxide (which had a pH of 2 inwater) was placed in a crucible with the lid ajar and was calcined at800° C. (with air flow) for 3 hours. The pH of the catalyst in water was3.

EXAMPLE 33 Treatment Of Sulfate-Bound Zirconium Oxide Catalyst WithSodium Hydroxide

3.85 g of sulfate-bound zirconium oxide catalyst (which had a pH of 2 inwater) was treated with 50 ml of 0.5N NaOH solution in a beaker withstirring for about 1 minute. (The catalyst had been prepared by theprocedure of Example 1.) The admixture was filtered. The solid filtratewas calcined in a Pyrex tube at 575° C. (with air flow) for 1 hour. ThepH of the calcined catalyst in water was 9.

EXAMPLE 34 Preparation of CARBOWAX® Polyethylene Glycol Using BasicSulfate-Bound Zirconium Oxide Catalyst

40.1 g of ethylene glycol and 5.0 g of the basic sulfate-bound zirconiumoxide catalyst of Example 33 were charged to a Parr bomb. The bomb waspurged with N₂ and evacuated three times. The bomb was left under 16p.s.i.g. of N₂. The bomb was heated about 85° C. and stirred vigorously.The pH of the material in the bomb was 5 to 6. Ethylene oxide wascharged to the bomb based on the following schedule:

                  TABLE XXII                                                      ______________________________________                                                             Reactor  Total Ethylene                                  Time,   Reactor      Pressure Oxide Feed,                                     Mins.   Temp., °C.                                                                          p.s.i.g. grams                                           ______________________________________                                         0       85°  18/46    5.9                                              25     105°  23/54    9.5                                              43     110°  24/56    13.8                                             63     112°  25/50    16.7                                             73     110°  30/58    19.1                                             85     112°  32/54    20.6                                             98     111°  28/58    22.7                                            106     111°  33 (1)                                                   106     115°  25/54    27.4                                            151     110°  27/64    31.5                                            206     110°  28/62    35.5                                            247     110°  33/68    40.5                                            406     108°  30                                                       ______________________________________                                         Note:                                                                         (1) The reactor heat was cut off and the reactor sat overnight.          

No exotherm was noticed after the first ethylene oxide addition. Afterthe second ethylene oxide addition, there was an exotherm to 123° C. butthere was no reaction after 5 minutes because there was no pressuredrop. The pressure was increased to 110° C. and there was an exotherm to114° C. The reactor was shut down after the run. The catalyst wasfiltered out of the liquid product and placed in a test tube.

EXAMPLE 35 Hydrolysis Of Zirconyl Acetate To Produce Sulfate-BoundZirconium Oxide Catalyst

30 g of (NH₄)₂ SO₄ were dissolved in 100 ml of distilled water. 11.26 gof zirconyl acetate, i.e., ZrO(OAc)₂ where OAc is C₂ H₃ O₂, was added tothe solution. An additional 50 ml of distilled water was added. At thispoint, the pH of the solution was 4 to 5. A total of 9.5 ml of 4M NaOHwas added to the solution to raise the pH to 9. The solid material wasfiltered out of the solution and washed with acetone. The solid wascalcined in Pyrex tubes at 575° C. (with air flow) for 3.5 hours. The pHof the calcined solid in water was 1. 2 grams of the calcined materialwas set aside for later use. The remainder of the calcined material waswashed with about 200 ml of distilled water and then rinsed with acetoneto dry it. The material was then calcined in a Pyrex tube at 520° C.(with air flow) for 23 hours. The pH of the solid in water was 1 to 2.The solid was sulfate-bound zirconium oxide catalyst.

EXAMPLE 36 Preparation of CARBOWAX® Polyethylene Glycol UsingSulfate-Bound Zirconium Oxide Catalyst

40.0 g of ethylene glycol and 2.0 g of sulfate-bound zirconium oxidecatalyst (that which was set aside in Example 35 for a later use) werecharged to a Parr bomb. The bomb was purged with N₂ and evacuated threetimes. The bomb was left under 16 p.s.i.g. of N₂. The bomb was heated toabout 80° C. and stirred vigorously. The pH of the material in the bombinitially was 5, but the pH stick slowly changed to 2. Ethylene oxidewas charged to the bomb based on the following schedule:

                  TABLE XXIII                                                     ______________________________________                                                         Reactor  Total Ethylene                                                                          Top Of                                    Time, Reactor    Pressure,                                                                              Oxide Feed,                                                                             Exotherm,                                 Mins. Temp., °C.                                                                        p.s.i.g. grams     °C.                                ______________________________________                                         0     82°                                                                              20/42    5.7       108°                                4     91°                                                                              29/50    10.6      (1)                                       11     91°                                                                              30/45    16.0      (1)                                       25    108°                                                                              28/55    20.0      128°                               31    110°                                                                              32/55    23.6      119°                               37    103°                                                                              32/60    27.5        130°(1)                          47    112°                                                                              34/60    30.2        124°(1)                          54    112°                                                                              36/60    34.7        117°(1)                          67    109°                                                                              34/60    40.0                                                99    114°                                                                              34                                                           ______________________________________                                    

An exotherm was observed upon the first ethylene oxide addition, and thereaction rate was fairly fast. At the 25 minute addition, the reactiontemperature was raised to about 110° C. Thereafter, mild exothermsoccurred and the reaction rate remained fairly fast. After the reactorwas closed down, the catalyst was filtered out of the liquid product anddiscarded. The pH of the liquid product was 5. The liquid product wasanalyzed using vapor phase chromatography. The CARBOWAX® polyethyleneglycol product contained a large amount of undesirable 1,4-dioxane.

EXAMPLE 37 Hydrolysis Of Hafnyl Chloride To Product Sulfate-Bound HafnylOxide Catalyst

16.4 g of HfOCl₂.8H₂ O were dissolved in 100 ml of distilled water. ThepH of the solution was 0 to 1. Concentrated NH₄ OH was added, withstirring, until the solution pH reached 9 and a white, gelatinousprecipitate formed. 6 ml of NH₄ OH were added to the solution, which wasstirred for 10 minutes. The product precipitated out of the solution.The solid filtrate was washed overnight in a Soxhlet extractor withdistilled water. The wash water in the Soxhlet extractor with thecatalyst has a pH of 7 and was negative for Cl⁻ (AgNO₃ test). The washwater in the flask has a pH of 7 and tested positive for Cl⁻. The solidwas dried in an open beaker set in an oven (100° to 120° C.) for about24 hours. 7.05 g of solid was obtained. The solid was treated with 106ml of 1NH₂ SO₄ in a beaker with stirring for about 5 minutes. The solidwas dried overnight at 110° to 120° C. The pH of the solid in water was2. The solid was calcined in a Pyrex tube at 575° C. (with air flow) for4.5 hours. The resultant fine white powder had a pH of 1 in water. Thesolid was sulfate-bound hafnyl oxide catalyst.

EXAMPLE 38 Preparation of CARBOWAX® Polyethylene Glycol UsingSulfate-Bound Hafnyl Oxide Catalyst

40.0 g of ethylene glycol and 2.0 g of sulfate-bound hafnyl oxidecatalyst (as prepared in Example 38) were charged to a Parr bomb. Thebomb was purged with N₂ and evacuated three times. The bomb was leftunder 16 p.s.i.g. of N₂. The pH of the material in the bomb was 3 (andwas slow to change). The bomb was heated to 100° C. and stirredvigorously. Ethylene oxide was added to the bomb based on the followingschedule:

                  TABLE XXIV                                                      ______________________________________                                                         Reactor  Total Ethylene                                                                          Top Of                                    Time, Reactor    Pressure,                                                                              Oxide Feed,                                                                             Exotherm,                                 Mins. Temp., °C.                                                                        p.s.i.g. grams     °C.                                ______________________________________                                         0    100°                                                                              21/46    5.4       134°                                3    110°                                                                              28/50    10.2      136°                                5    111°                                                                              29/50    15.1      135°                                8    111°                                                                              30/50    20.2      135°                               10    111°                                                                              30/50    25.3      130°                               13    109°                                                                              32/50    30.1      124°                               16    109°                                                                              33/50    33.0      116°                               20    111°                                                                              33/50    35.4      115°                               23    110°                                                                              34/52    37.7      113°                               25    109°                                                                              35/50    40.0      (1)                                       49    110°                                                                              35                                                           ______________________________________                                         Note:                                                                         (1) No exotherm.                                                         

The reaction was run at 100° to 110° C. Fairly large exotherms occurredrun when ethylene oxide was added. The reaction rate was very fast (whencompared to the fastest zirconium compound catalyst tested in the aboveexamples). The catalyst was filtered from the product, and washed withabout 25 ml of methanol. The catalyst was placed in a Pyrex test tubeand placed in a 530° C. oven (with air flow) for about 12 days. Theliquid product was analyzed using vapor phase chromatography. Theproduct contained a fairly large amount of dioxane. The product wasCARBOWAX® polyethylene glycol produced by ethoxylation of ethyleneglycol.

What is claimed is:
 1. Process comprising reacting at least one moleculeof a liquid or solid epoxide compound having the formula: ##STR10##wherein R₁, R₂, R₃ and R₄ are each H or --(CH₂)_(n) CH₃, and wherein nis 0 to 3, with the proviso that R₁, R₂, R₃ and R₄ are the same ordifferent, with at least one other molecule of said epoxide compound inthe presence of catalytic amount of at least one solid anion-bound metaloxide heterogeneous catalyst, wherein said anion in said anion-boundmetal oxide heterogeneous catalyst is SO₄, BF₄, CO₃, BO₃, HPO₄, SeO₄,MoO₄, B₄ O₇ or PF₆, and the metal oxide is zirconium oxide, nickeloxide, aluminum oxide, tin oxide, magnesium oxide, iron oxide, titaniumoxide, thorium oxide, hafnium oxide or rubidium oxide, said anion-boundmetal oxide heterogeneous catalyst being an amorphous or primarilyamorphous compound, and said molecules of said epoxide compound beingthe same epoxide compound or different epoxide compounds.
 2. Process asclaimed in claim 1 wherein 0.5 to 50 weight percent, based on the totalweight of said epoxide compound, of said anion-bound metal oxidecatalyst is used.
 3. Process as claimed in claim 1 wherein saidanion-bound metal oxide catalyst is an anion-bound zirconium oxidecatalyst, an anion-bound nickel oxide catalyst, an anion-bound aluminumoxide catalyst, an anion-bound tin oxide catalyst, an anion-boundcalcium oxide catalyst, an anion-bound magnesium oxide catalyst, ananion-bound rubidium oxide catalyst, an anion-bound titanium oxidecatalyst, an anion-bound thorium oxide catalyst, an anion-bound hafniumoxide catalyst, or an anion-bound iron oxide catalyst.
 4. Process asclaimed in claim 1 wherein said catalyst is a solid anion-boundzirconium oxide catalyst.
 5. Process as claimed in claim 4 wherein saidsolid anion-bound zirconium oxide catalyst contains about 2 to about 3weight percent, based on the total weight of said catalyst, of saidanion.
 6. Process as claimed in claim 5 wherein said catalyst is ananion-bound thorium oxide catalyst.
 7. Process as claimed in claim 1wherein said catalyst is a solid sulfate-bound hafnium oxide catalyst.8. Process as claimed in claim 1 wherein said catalyst is supported onan inert carrier.
 9. Process as claimed in claim 1 wherein an inertliquid diluent is also present.
 10. Process as claimed in claim 1wherein the epoxide compound is ethylene oxide, or propylene oxide. 11.Process as claimed in claim 1 wherein said reaction is continuouslyconducted in a fluidized reactor.
 12. Process as claimed in claim 1wherein said anion-bound metal oxide is removed from the reaction siteand is regenerated by calcination in air or oxygen at a temperature of300° to 950° C. for a period of 1 to 4 hours.